TW201606050A - Ceramic composite material for optical conversion, production method therefor, and light-emitting device provided with same - Google Patents

Ceramic composite material for optical conversion, production method therefor, and light-emitting device provided with same Download PDF

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TW201606050A
TW201606050A TW104108724A TW104108724A TW201606050A TW 201606050 A TW201606050 A TW 201606050A TW 104108724 A TW104108724 A TW 104108724A TW 104108724 A TW104108724 A TW 104108724A TW 201606050 A TW201606050 A TW 201606050A
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Taiwan
Prior art keywords
light
ceramic composite
phase
light conversion
powder
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TW104108724A
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Chinese (zh)
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TWI624529B (en
Inventor
Shiyohei Asai
Masataka Yamanaga
Kazuki Kuwahara
Yuki Nagao
Koji Shibata
Takafumi Kawano
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Ube Industries
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Abstract

The present invention addresses the problem of providing: a ceramic composite material for optical conversion that exhibits excellent heat resistance, durability, and the like as an optical conversion member for an optical device such as a white light-emitting diode, that makes it easy to adjust the ratio of light from a light source and fluorescence, that is capable of reducing uneven color and irregularity in emitted light, and that has high internal quantum efficiency and high fluorescence intensity; a production method therefor; and a light-emitting device that is provided with same and that has high optical conversion efficiency. Provided is a ceramic composite material for optical conversion that is configured from a fluorescence phase and a light-transmitting phase and that is characterized in that the fluorescence phase is a phase containing Ln3Al5O12:Ce (Ln is at least one element selected from among Y, Lu, and Tb, and Ce is an activation element) and the light-transmitting phase is a phase containing LaAl11O18.

Description

光轉換用陶瓷複合材料、其製造方法、及具備其之發光裝置 Ceramic composite material for light conversion, method for producing the same, and light-emitting device therewith

本發明係關於一種可利用於顯示器、照明、及背光光源等之發光二極體等發光裝置所使用之光轉換用陶瓷複合材料、其製造方法、及具備其之發光裝置。 The present invention relates to a ceramic composite for light conversion used in a light-emitting device such as a light-emitting diode such as a display, an illumination, or a backlight source, a method for producing the same, and a light-emitting device including the same.

近年來，積極地進行以藍色發光元件為發光源之白色發光裝置之開發研究。特別是，使用藍色發光二極體元件之白色發光二極體係輕量、不使用水銀、且壽命長，因此預測今後之需要會急速地擴大。再者，將使用發光二極體元件作為發光元件之發光裝置稱為發光二極體。作為將藍色發光二極體元件之藍色光轉換為白色光之方法，最普遍進行之方法係如下者：藉由混合與藍色為補色關係之黃色而類似地獲得白色。例如，如專利文獻1所記載，於發出藍色光之二極體元件之整個面，設置含有吸收藍色光之一部分並發出黃色光之螢光體之塗層，並於塗層之上設置將光源之藍色光與來自螢光體之黃色光混色之模層等，藉此可構成白色發光二極體。作為螢光體，使用藉由鈰而活化之YAG(Y3Al5O12)(以下，記為YAG：Ce)粉末等。 In recent years, research and development of a white light-emitting device using a blue light-emitting element as a light-emitting source has been actively conducted. In particular, the white light-emitting diode system using the blue light-emitting diode element is lightweight, does not use mercury, and has a long life. Therefore, it is predicted that the future needs will be rapidly expanded. Further, a light-emitting device using a light-emitting diode element as a light-emitting element is referred to as a light-emitting diode. As a method of converting blue light of a blue light-emitting diode element into white light, the most common method is to obtain white similarly by mixing yellow with a complementary color of blue. For example, as described in Patent Document 1, a coating layer containing a phosphor that absorbs a part of blue light and emits yellow light is provided on the entire surface of the diode element that emits blue light, and a light source is disposed on the coating layer. The blue light is mixed with the yellow light from the phosphor, and the like, thereby forming a white light-emitting diode. As the phosphor, YAG (Y 3 Al 5 O 12 ) (hereinafter referred to as YAG: Ce) powder activated by hydrazine is used.

然而，有人指出，專利文獻1所代表之目前普遍使用之白色 發光二極體之構造係將螢光體粉末與環氧樹脂等樹脂混合而塗佈，故而確保了螢光體粉末與樹脂之混合狀態之均勻性、及塗佈膜之厚度之穩定化等之控制較為困難，易於產生白色發光二極體之色不均、偏差。又，無論為了塗佈螢光體粉末、抑或為了不對光源之一部分藍色光進行光轉換而使該藍色光穿透塗佈膜而均需求的具有透光性之樹脂係耐熱性較差，故而易由來自發光元件之熱導致變性並因該變性而引起穿透率下降。因此，成為目前要求之白色發光二極體之高輸出化之瓶頸。 However, it has been pointed out that the white color currently used in Patent Document 1 is generally used. In the structure of the light-emitting diode, the phosphor powder is mixed with a resin such as an epoxy resin, and the uniformity of the mixed state of the phosphor powder and the resin, and the stabilization of the thickness of the coating film are ensured. Control is difficult, and it is easy to produce color unevenness and deviation of white light-emitting diodes. Further, the resin having light transmissivity required for the application of the phosphor powder or the light transmissing of the blue light to the light source is inferior in heat resistance, so that it is easy to be used. The heat from the light-emitting element causes denaturation and a decrease in transmittance due to the denaturation. Therefore, it has become a bottleneck for the high output of the currently required white light-emitting diode.

因此，進行作為白色發光二極體等光器件之光轉換構件不使用樹脂而構成之具有螢光相之無機系光轉換材料的研究，又，進行將該材料用作光轉換構件之光器件之研究。 Therefore, research has been conducted on an inorganic light-converting material having a fluorescent phase which is not used as a light-converting member of an optical device such as a white light-emitting diode, and an optical device using the material as a light-converting member is performed. the study.

例如，於專利文獻2中，揭示有如下波長轉換構件：將通式M3(Al1-vGav)5O12：Ce(於式中，M為選自Lu、Y、Gd、及Tb中之至少一種，v滿足0≦v≦0.8)表示之藉由鈰(Ce)而活化的鋁酸鹽螢光體粉末與玻璃材料混合，並使玻璃材料溶融，藉此使螢光體粉末分散於玻璃材料中而獲得。 For example, Patent Document 2 discloses a wavelength converting member having a general formula M 3 (Al 1-v Ga v ) 5 O 12 :Ce (wherein M is selected from the group consisting of Lu, Y, Gd, and Tb) At least one of, v satisfies 0≦v≦0.8), the aluminate phosphor powder activated by cerium (Ce) is mixed with the glass material, and the glass material is melted, thereby dispersing the phosphor powder Obtained in glass materials.

又，於專利文獻3中，揭示有藉由燒結而獲得之具有螢光體相及基材相之陶瓷複合體，該螢光體相係由含有Ce之YAG所構成，該基材相係由Al2O3等透光性陶瓷所構成。 Further, Patent Document 3 discloses a ceramic composite having a phosphor phase and a substrate phase obtained by sintering, the phosphor phase being composed of YAG containing Ce, which is composed of It is composed of a translucent ceramic such as Al 2 O 3 .

[先前技術文獻] [Previous Technical Literature]

[專利文獻] [Patent Literature]

[專利文獻1]日本特開2000-208815號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-208815

[專利文獻2]日本特開2008-041796號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-041796

[專利文獻3]日本特開2012-062459號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2012-062459

然而，專利文獻2所記載之波長轉換構件存在如下問題：由於基材為玻璃，故而雖耐熱性、耐久性得到改善，但難以使螢光體粉末均勻地分散於作為基材之玻璃，於放射之光中易產生色不均、或因放射角度引起之偏差。 However, the wavelength conversion member described in Patent Document 2 has a problem in that heat resistance and durability are improved because the base material is glass, but it is difficult to uniformly disperse the phosphor powder in the glass as a base material. The light is prone to color unevenness or deviation due to the radiation angle.

又，專利文獻3所記載之陶瓷複合體係基材(透光相)為陶瓷，且並非於透光相分散有螢光體粉末之構造，因此不存在耐熱性、耐久性等問題，且亦不存在螢光體粉末之分散性之問題，但光學特性之提高需要進一步之改良。 Further, since the ceramic composite system substrate (transmissive phase) described in Patent Document 3 is a ceramic and does not have a structure in which a phosphor powder is dispersed in a light-transmitting phase, there is no problem such as heat resistance and durability, and There is a problem of dispersibility of the phosphor powder, but improvement in optical characteristics requires further improvement.

因此，本發明之目的在於提供一種作為白色發光二極體等光器件之光轉換構件而耐熱性、耐久性等優異、光源之光與螢光之比率調節較為容易、且可減少放射光之色不均或偏差、進而具有較高之內部量子效率及螢光強度的光轉換用陶瓷複合材料、其製造方法、及具備其之光轉換效率較高之發光裝置。 Therefore, an object of the present invention is to provide a light-converting member of an optical device such as a white light-emitting diode, which is excellent in heat resistance, durability, and the like, and it is easy to adjust the ratio of light to fluorescence of a light source, and can reduce the color of emitted light. A ceramic composite material for light conversion which has uneven internal density and high internal quantum efficiency and fluorescence intensity, a method for producing the same, and a light-emitting device having high light conversion efficiency.

本發明人等為了解決上述課題已進行潛心研究，結果發現：由含有Ln3Al5O12：Ce(Ln為選自Y、Lu、及Tb中之至少一種元素，Ce為活化元素)之螢光相、及含有LaAl11O18之透光相所構成之光轉換用陶瓷複合 材料具有較高之內部量子效率及螢光強度，又，發現：使用該光轉換用陶瓷複合材料之發光裝置其光轉換效率較高，從而完成本發明。 The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that a firefly containing Ln 3 Al 5 O 12 :Ce (Ln is at least one selected from the group consisting of Y, Lu, and Tb, and Ce is an active element) The optical composite ceramic composite material composed of the optical phase and the light-transmissive phase containing LaAl 11 O 18 has high internal quantum efficiency and fluorescence intensity, and it has been found that the light-emitting device using the ceramic composite for light conversion has The light conversion efficiency is high, thereby completing the present invention.

即，本發明係關於一種光轉換用陶瓷複合材料，由螢光相及透光相所構成，其特徵在於：上述螢光相為含有Ln3Al5O12：Ce(Ln為選自Y、Lu、及Tb中之至少一種元素，Ce為活化元素)之相，上述透光相為含有LaAl11O18之相。 That is, the present invention relates to a ceramic composite for light conversion, comprising a fluorescent phase and a light transmissive phase, wherein the fluorescent phase contains Ln 3 Al 5 O 12 :Ce (Ln is selected from Y, Lu, and Tb and is at least one element, Ce as an activator element) of the phase, containing the above-described light-transmissive phase relative of LaAl 11 O 18.

於本發明中，上述螢光相較佳為含有(Ln,La)3Al5O12：Ce(Ln為選自Y、Lu、及Tb中之至少一種元素，Ce為活化元素)之相。 In the present invention, the fluorescent phase is preferably a phase containing (Ln, La) 3 Al 5 O 12 :Ce (Ln is at least one element selected from the group consisting of Y, Lu, and Tb, and Ce is an activating element).

又，上述透光相較佳為於透光相中含有9~100質量%之LaAl11O18之相。 Further, the light-transmitting phase is preferably a phase containing 9 to 100% by mass of LaAl 11 O 18 in the light-transmitting phase.

又，上述透光相較佳為進而含有選自α-Al2O3及LaAlO3中之至少一種之相。 Moreover, it is preferable that the light-transmitting phase further contains a phase selected from at least one of α-Al 2 O 3 and LaAlO 3 .

又，上述光轉換用陶瓷複合材料較佳為於燒成後，在非活性氣體環境或還原性氣體環境中以1000~2000℃受到熱處理。 Moreover, it is preferable that the ceramic composite for light conversion is subjected to heat treatment at 1000 to 2000 ° C in an inert gas atmosphere or a reducing gas atmosphere after firing.

又，本發明係關於一種發光裝置，其具備發光元件及上述記載之光轉換用陶瓷複合材料。 Moreover, the present invention relates to a light-emitting device comprising a light-emitting element and the above-described ceramic composite for light conversion.

又，本發明係關於一種發光裝置，具備：發光元件，其於波長420~500nm具有波峰；及如上述記載之光轉換用陶瓷複合材料，其發出於540~580nm具有主波長之螢光。 Furthermore, the present invention relates to a light-emitting device comprising: a light-emitting element having a peak at a wavelength of 420 to 500 nm; and the ceramic composite for light conversion as described above, which emits fluorescence having a dominant wavelength of 540 to 580 nm.

於本發明中，較佳為上述發光元件為發光二極體元件。 In the invention, it is preferable that the light-emitting element is a light-emitting diode element.

又，本發明係關於一種光轉換用陶瓷複合材料之製造方法，具備如下步驟：煅燒步驟，其係對含有Al源化合物、Ln源化合物(Ln為 選自Y、Lu、及Tb中之至少一種元素)、及Ce源化合物之混合粉末進行煅燒；及燒成步驟，其係將對上述煅燒步驟中所獲得之煅燒粉末100質量%添加有以氧化物換算計為1~50質量%之La源化合物的含La混合粉末進行燒成。 Further, the present invention relates to a method for producing a ceramic composite for light conversion, comprising the steps of: a calcination step comprising an Al source compound and an Ln source compound (Ln is a mixed powder of at least one selected from the group consisting of Y, Lu, and Tb) and a Ce source compound, and a calcination step of adding 100% by mass of the calcined powder obtained in the calcination step to oxidize The La-containing mixed powder of the La source compound in an amount of from 1 to 50% by mass is calcined.

於本發明中，較佳為於上述燒成步驟後具備熱處理步驟，該熱處理步驟係於非活性氣體環境或還原性氣體環境中以1000~2000℃進行熱處理。 In the present invention, it is preferred to provide a heat treatment step after the calcination step, wherein the heat treatment step is performed at 1000 to 2000 ° C in an inert gas atmosphere or a reducing gas atmosphere.

又，上述含La混合粉末較佳為於藉由選自壓製成形法、片成形法、及擠壓成形法中之至少一種成形法而成形後被燒成。 Moreover, it is preferable that the La-containing mixed powder is formed by at least one molding method selected from the group consisting of a press molding method, a sheet molding method, and an extrusion molding method, and then fired.

根據本發明，可提供一種作為白色發光二極體等光器件之光轉換構件而耐熱性、耐久性等優異、光源之光與螢光之比率調節較為容易、可減少放射光之色不均或偏差、進而具有較高之內部量子效率及螢光強度的光轉換用陶瓷複合材料及其製造方法。 According to the present invention, it is possible to provide a light-converting member as an optical device such as a white light-emitting diode, which is excellent in heat resistance, durability, and the like, and it is easy to adjust the ratio of light to fluorescence of a light source, and it is possible to reduce color unevenness of emitted light or A ceramic composite for light conversion, which has a high internal quantum efficiency and a fluorescent intensity, and a method for producing the same.

又，可提供一種不使用因光或熱而劣化之樹脂等，而可由無機結晶質物質構成發光二極體等光器件之光轉換部之透光相、壽命長且光轉換效率較高之發光裝置。 Further, it is possible to provide a light-transmissive phase in which a light-converting portion of an optical device such as a light-emitting diode can be formed of an inorganic crystalline substance without using a resin which is deteriorated by light or heat, and has a long life and a high light conversion efficiency. Device.

圖1係表示(a)實施例21、(b)實施例18、及(c)比較例3之SEM照片之圖。 Fig. 1 is a view showing SEM photographs of (a) Example 21, (b) Example 18, and (c) Comparative Example 3.

圖2係表示(a)實施例35及(b)比較例3之螢光相粒子與透光相粒 子之界面部分之暗視野STEM照片的圖。 Figure 2 is a diagram showing the fluorescent phase particles and the light-transmitting phase particles of (a) Example 35 and (b) Comparative Example 3. A picture of a dark field STEM photograph of the interface portion of the sub-port.

以下，詳細地對本發明進行說明。 Hereinafter, the present invention will be described in detail.

(光轉換用陶瓷複合材料) (ceramic composite for light conversion)

本發明之光轉換用陶瓷複合材料由螢光相及透光相所構成，其特徵在於：上述螢光相為含有Ln3Al5O12：Ce(Ln為選自Y、Lu、及Tb中之至少一種元素，Ce為活化元素)之相，上述透光相為含有LaAl11O18之相。 The ceramic composite for light conversion according to the present invention comprises a fluorescent phase and a light transmissive phase, wherein the fluorescent phase contains Ln 3 Al 5 O 12 :Ce (Ln is selected from the group consisting of Y, Lu, and Tb). The phase of at least one element, Ce is an activating element, and the light transmissive phase is a phase containing LaAl 11 O 18 .

本發明之光轉換用陶瓷複合材料由螢光相及透光相所構成，該螢光相係將所接收到之光轉換為不同波長之光並發出、即具有螢光性；該透光相係不將所接收到之光轉換為不同波長之光而直接使該所接收到之光穿透。藉由調節上述螢光相與上述透光相之比率，可調節藉由螢光相而轉換之光、與不轉換而穿透透光相之光之比率，從而可調節將本發明之光轉換用陶瓷複合材料用作光轉換部之光器件所發出之光的色度。 The ceramic composite material for light conversion of the present invention comprises a fluorescent phase and a light transmissive phase, and the fluorescent phase converts the received light into light of different wavelengths and emits light, that is, has fluorescence; The received light is not directly transmitted by converting the received light into light of different wavelengths. By adjusting the ratio of the fluorescent phase to the light transmissive phase, the ratio of the light converted by the fluorescent phase to the light transmissive to the transparent phase can be adjusted, thereby adjusting the light conversion of the present invention. The ceramic composite is used as the chromaticity of light emitted by the optical device of the light conversion portion.

於本發明之光轉換用陶瓷複合材料中，螢光相之比率較佳為10~90質量%。其原因在於，若為該範圍之比率，則可較高地保持光轉換用陶瓷複合材料之光轉換效率，又，於應用於光器件之光轉換部時，不會發生光轉換用陶瓷複合材料之厚度變得過小而處理變得困難之情況。根據相同之觀點，螢光相之比率更佳為20~85質量%，進而較佳為30~80質量%，特佳為40~75質量%。又，本發明之光轉換用陶瓷複合材料較佳為僅由上述螢光相及上述透光相構成。 In the ceramic composite for light conversion of the present invention, the ratio of the fluorescent phase is preferably from 10 to 90% by mass. The reason for this is that the light conversion efficiency of the ceramic composite for light conversion can be maintained high in the ratio of the range, and the ceramic composite for light conversion does not occur when applied to the light conversion portion of the optical device. The case where the thickness becomes too small and the handling becomes difficult. From the same viewpoint, the ratio of the fluorescent phase is more preferably from 20 to 85% by mass, further preferably from 30 to 80% by mass, particularly preferably from 40 to 75% by mass. Moreover, it is preferable that the ceramic composite for light conversion of the present invention comprises only the above-mentioned fluorescent phase and the above-mentioned light transmitting phase.

於本發明中，螢光相含有Ln3Al5O12：Ce(Ln為選自Y、Lu、 及Tb中之至少一種元素，Ce為活化元素)。Ln可為選自Y、Lu、及Tb中之一種元素，亦可為該等多個元素。又，螢光相之Ln3Al5O12：Ce較佳為(Ln,La)3Al5O12：Ce(Ln為選自Y、Lu、及Tb中之至少一種元素，Ce為活化元素)。再者，於本發明中，表記為(Ln,La)3Al5O12：Ce之化學式係意味著(Ln,La)3Al5O12：Ce含有Ln及La。Ln3Al5O12：Ce可進而含有Gd等Ln及Ce以外之稀土元素或Ga，例如於含有Gd之情形時，可使自螢光相發出之螢光之波長有效率地長波長化。 In the present invention, the fluorescent phase contains Ln 3 Al 5 O 12 :Ce (Ln is at least one element selected from the group consisting of Y, Lu, and Tb, and Ce is an activating element). Ln may be one element selected from the group consisting of Y, Lu, and Tb, and may be the plurality of elements. Further, the fluorescent phase of Ln 3 Al 5 O 12 :Ce is preferably (Ln,La) 3 Al 5 O 12 :Ce (Ln is at least one element selected from the group consisting of Y, Lu, and Tb, and Ce is an activating element ). Further, in the present invention, denoted as (Ln, La) 3 Al 5 O 12: Ce -based means of chemical formula (Ln, La) 3 Al 5 O 12: Ce and Ln contains La. Ln 3 Al 5 O 12 :Ce may further contain a rare earth element other than Ln and Ce such as Gd or Ga. For example, when Gd is contained, the wavelength of the fluorescent light emitted from the fluorescent phase can be efficiently increased in wavelength.

於本發明中，透光相為由不將所接收到之光轉換為不同波長之光而使其以原來之波長穿透之結晶所構成之相，且含有LaAl11O18、及作為任意成分之選自α-Al2O3及LaAlO3中之至少一種。構成透光相之各結晶可為連續之一個相，亦可由多個晶粒所構成。例如，於本發明之透光相由LaAl11O18及α-Al2O3所構成之情形時，亦可由多個LaAl11O18晶粒及多個α-Al2O3晶粒所構成。 In the present invention, the light-transmitting phase is a phase composed of crystals which do not convert the received light into light of different wavelengths and penetrate the original wavelength, and contains LaAl 11 O 18 and as an optional component. It is selected from at least one of α-Al 2 O 3 and LaAlO 3 . Each of the crystals constituting the light-transmitting phase may be one continuous phase or may be composed of a plurality of crystal grains. For example, when the light transmissive phase of the present invention is composed of LaAl 11 O 18 and α-Al 2 O 3 , it may be composed of a plurality of LaAl 11 O 18 crystal grains and a plurality of α-Al 2 O 3 crystal grains. .

上述透光相中，LaAl11O18之比率較佳為9~100質量%。又，上述透光相中，除LaAl11O18以外，亦可含有選自α-Al2O3及LaAlO3中之至少一種。上述透光相中，α-Al2O3之比率較佳為0~91質量%。又，上述透光相中，LaAlO3之比率較佳為0~21質量%。根據以上之構成，本發明之光轉換用陶瓷複合材料具有較高之內部量子效率及螢光強度。 In the above light-transmitting phase, the ratio of LaAl 11 O 18 is preferably from 9 to 100% by mass. Further, the light-transmitting phase may contain at least one selected from the group consisting of α-Al 2 O 3 and LaAlO 3 in addition to LaAl 11 O 18 . In the light-transmitting phase, the ratio of α-Al 2 O 3 is preferably from 0 to 91% by mass. Further, the transparent phase, LaAlO 3 ratio of preferably 0 to 21 mass%. According to the above configuration, the ceramic composite for light conversion of the present invention has high internal quantum efficiency and fluorescence intensity.

特別是，上述透光相更佳為上述透光相中之LaAl11O18之比率為70~100質量%，且上述透光相中之α-Al2O3之比率為0~30質量%，或者，上述透光相中之LaAl11O18之比率為95~100質量%，且上述透光相中之LaAlO3之比率為0~5質量%。若上述透光相為以上之構成，則本發明之光 轉換用陶瓷複合材料具有特別高之內部量子效率及螢光強度。 In particular, the light transmissive phase is preferably such that the ratio of LaAl 11 O 18 in the light transmissive phase is 70 to 100% by mass, and the ratio of α-Al 2 O 3 in the light transmissive phase is 0 to 30% by mass. or, the above-described light-transmitting LaAl 11 O 18 phase, the ratio of 95 to 100% by mass, and the above-described light-transmissive phase of LaAlO 3 ratio of from 0 to 5 mass%. When the light-transmitting phase is the above configuration, the ceramic composite for light conversion of the present invention has particularly high internal quantum efficiency and fluorescence intensity.

上述透光相中之LaAl11O18之比率越大，則本發明之光轉換用陶瓷複合材料之內部量子效率及螢光強度越高。因此，上述透光相特佳為實質上僅由LaAl11O18所構成。本發明之LaAl11O18為化學式LaAl11O18表示之六方晶系鑭鋁氧化物。又，作為類似化合物，可列舉La2Al24.4O39.6、La0.9Al11.76O19、La1.4Al22.6O36、La0.827Al11.9O19.09、La0.9Al11.95O18.9、La0.85Al11.5O18.5、La0.85Al11.55O18.6、La0.85Al11.6O18.675表示之六方晶系鑭鋁氧化物，藉由該等鑭鋁氧化物亦可獲得相同之效果。此處，上述透光相實質上僅由LaAl11O18所構成之本發明之光轉換用陶瓷複合材料亦可按照不會對內部量子效率及螢光強度造成影響之程度含有LaAl11O18以外之成分。 The larger the ratio of LaAl 11 O 18 in the light-transmitting phase, the higher the internal quantum efficiency and the fluorescence intensity of the ceramic composite for light conversion of the present invention. Therefore, the above-mentioned light transmissive phase is particularly preferably composed of only LaAl 11 O 18 . The LaAl 11 O 18 of the present invention is a hexagonal yttrium aluminum oxide represented by the chemical formula LaAl 11 O 18 . Further, examples of the similar compound include La 2 Al 24.4 O 39.6 , La 0.9 Al 11.76 O 19 , La 1.4 Al 22.6 O 36 , La 0.827 Al 11.9 O 19.09 , La 0.9 Al 11.95 O 18.9 , and La 0.85 Al 11.5 O 18.5 . La 0.85 Al 11.55 O 18.6 , La 0.85 Al 11.6 O 18.675 represents a hexagonal yttrium aluminum oxide, and the same effect can be obtained by the ruthenium aluminum oxide. Here, the light-transmissive phase ceramic composite material for light conversion of the present invention which is substantially composed only of LaAl 11 O 18 may contain LaAl 11 O 18 to such an extent that it does not affect the internal quantum efficiency and the fluorescence intensity. The ingredients.

於上述透光相中之LaAl11O18之比率較多之情形時，螢光相中一部分La固溶，而螢光相之Ln3Al5O12：Ce成為(Ln,La)3Al5O12：Ce(Ln為選自Y、Lu、及Tb中之至少一種元素，Ce為活化元素)。如上所述，於透光相中之LaAl11O18之比率較多之情形時，具有較高之內部量子效率及螢光強度。因此，於螢光相之Ln3Al5O12：Ce為(Ln,La)3Al5O12：Ce之情形時，具有較高之內部量子效率及螢光強度。 When the ratio of LaAl 11 O 18 in the light-transmitting phase is large, a part of La in the fluorescent phase is solid-solved, and the fluorescent phase of Ln 3 Al 5 O 12 :Ce becomes (Ln, La) 3 Al 5 O 12 :Ce (Ln is at least one element selected from the group consisting of Y, Lu, and Tb, and Ce is an activating element). As described above, when the ratio of LaAl 11 O 18 in the light-transmitting phase is large, the internal quantum efficiency and the fluorescence intensity are high. Therefore, in the case where the fluorescent phase of Ln 3 Al 5 O 12 :Ce is (Ln,La) 3 Al 5 O 12 :Ce, it has high internal quantum efficiency and fluorescence intensity.

本發明之LaAl11O18有時含有Ln及/或Ce。又，於螢光相之Ln3Al5O12：Ce或(Ln,La)3Al5O12：Ce含有Ln及Ce以外之稀土元素之情形時，存在本發明之LaAl11O18含有Ln及Ce以外之上述稀土元素之情形。 The LaAl 11 O 18 of the present invention sometimes contains Ln and/or Ce. Further, in the case where the fluorescent phase of Ln 3 Al 5 O 12 :Ce or (Ln,La) 3 Al 5 O 12 :Ce contains a rare earth element other than Ln and Ce, the LaAl 11 O 18 of the present invention contains Ln. And the case of the above rare earth elements other than Ce.

又，本發明之光轉換用陶瓷複合材料存在如下情形：於不會對螢光特性造成影響之範圍內，含有作為螢光相而含有之Ln3Al5O12：Ce、作為透光相而含有之LaAl11O18、作為透光相之任意成分而含有之α-Al2O3及 LaAlO3以外之成分。作為該等成分，可列舉CeAlO3、CeAl11O18、及(Ln,Ce)AlO3等複合氧化物。又，於Ln3Al5O12：Ce含有Gd等Ln及Ce以外之稀土元素之情形時，例如於該稀土元素為Gd之情形時，本發明之光轉換用陶瓷複合材料除以上之成分以外，亦可含有Gd4Al2O9、GdAlO3、及(Ln,Ce,Gd)AlO3等成分。 Moreover, the ceramic composite material for light conversion of the present invention has a case where Ln 3 Al 5 O 12 :Ce which is contained as a fluorescent phase is contained in a range which does not affect the fluorescence characteristics, and is a light-transmitting phase. A component other than α-Al 2 O 3 and LaAlO 3 contained in LaAl 11 O 18 as an optional component of the light-transmitting phase. Examples of the components include composite oxides such as CeAlO 3 , CeAl 11 O 18 , and (Ln, Ce)AlO 3 . In the case where Ln 3 Al 5 O 12 :Ce contains a rare earth element other than Ln and Ce such as Gd, for example, when the rare earth element is Gd, the ceramic composite for light conversion of the present invention contains the above components. It may also contain components such as Gd 4 Al 2 O 9 , GdAlO 3 , and (Ln, Ce, Gd) AlO 3 .

構成本發明之光轉換用陶瓷複合材料的螢光相粒子及透光相粒子之粒徑較佳為1μm以上3.5μm以下，更佳為1.5μm以上3.5μm以下。於粒徑未達1μm之情形時，相對螢光強度、標準化光束變小，故而欠佳。又，於粒徑超過3.5μm之情形時，為了使粒徑變大，需要提高燒成溫度、且延長燒成時間，於製造方面欠佳。進而，於提高燒成溫度、且延長燒成時間之情形時，容易引起作為活化劑之Ce之濃度變化，故而欠佳。螢光相粒子及透光相粒子之粒徑可根據掃描式電子顯微鏡(SEM)照片，使用圖像解析軟體，求出粒子之等效圓直徑(Heywood徑)作為粒徑。 The particle diameter of the fluorescent phase particles and the light-transmitting phase particles constituting the ceramic composite material for light conversion of the present invention is preferably 1 μm or more and 3.5 μm or less, more preferably 1.5 μm or more and 3.5 μm or less. When the particle diameter is less than 1 μm, the relative fluorescence intensity and the normalized light beam become small, which is not preferable. Further, when the particle diameter exceeds 3.5 μm, in order to increase the particle diameter, it is necessary to increase the firing temperature and to extend the firing time, which is not preferable in terms of production. Further, when the firing temperature is increased and the baking time is prolonged, the concentration of Ce as an activator is likely to change, which is not preferable. The particle diameter of the fluorescent phase particles and the light-transmitting phase particles can be determined from a scanning electron microscope (SEM) photograph using an image analysis software to determine the equivalent circular diameter (Heywood diameter) of the particles.

於本發明中，上述透光相之LaAl11O18相之比率越多，則存在於上述透光相與上述螢光相之界面的Ce濃度越容易變小，而本發明之光轉換用陶瓷複合材料之內部量子效率及螢光強度越大。存在於透光相與螢光相之界面的Ce可利用掃描穿透式電子顯微鏡(STEM)之能量分散型X射線分光測定(EDS)而求出。作為界面之Ce濃度，較佳為3.5at%以下，更佳為1.0at%以下，進而較佳為0.5at%以下。 In the present invention, the more the ratio of the LaAl 11 O 18 phase of the light-transmitting phase, the more easily the Ce concentration at the interface between the light-transmitting phase and the fluorescent phase is, and the ceramic for light conversion of the present invention The internal quantum efficiency and fluorescence intensity of the composite material are greater. The Ce existing at the interface between the light-transmitting phase and the fluorescent phase can be obtained by energy dispersive X-ray spectrometry (EDS) of a scanning transmission electron microscope (STEM). The Ce concentration at the interface is preferably 3.5 at% or less, more preferably 1.0 at% or less, still more preferably 0.5 at% or less.

已知於存在有成為發光中心之元素以高濃度存在的區域之情形時，該區域之發光中心之光轉換效率變差，通常稱為濃度淬滅。又，一般認為，於Ce濃度較高之區域，螢光相與透光相之折射率差變大，易於 界面產生光散射，而光轉換效率下降。關於本發明之光轉換用陶瓷複合材料，推測，藉由透光相包含LaAl11O18相，而螢光相與透光相之界面之Ce濃度變高得到抑制，與先前之光轉換用陶瓷複合材料相比內部量子效率及螢光強度變大。 It is known that when there is a region where an element which becomes a luminescent center exists in a high concentration, the light conversion efficiency of the luminescent center of the region is deteriorated, and is generally referred to as concentration quenching. Further, it is considered that the refractive index difference between the fluorescent phase and the light-transmitting phase is large in a region where the Ce concentration is high, and light scattering is likely to occur at the interface, and the light conversion efficiency is lowered. In the ceramic composite material for light conversion of the present invention, it is presumed that the LaAl 11 O 18 phase is contained in the light-transmitting phase, and the Ce concentration at the interface between the fluorescent phase and the light-transmitting phase is suppressed, and the ceramic for light conversion is used. The composite material has an increased internal quantum efficiency and fluorescence intensity.

本發明之光轉換用陶瓷複合材料可藉由吸收於波長420~500nm具有波峰之光(激發光)，而高效率地發出於540~580nm具有主波長之螢光。藉此，可高效率地獲得黃色螢光。即便激發光為波長400~419nm、或者501~530nm，而效率下降，但本發明之光轉換用陶瓷複合材料可發出螢光。進而，即便激發光為波長300~360nm之近紫外光，本發明之光轉換用陶瓷複合材料亦可發出螢光。 The ceramic composite for light conversion of the present invention can efficiently emit light having a dominant wavelength of 540 to 580 nm by absorbing light having a peak at a wavelength of 420 to 500 nm (excitation light). Thereby, yellow fluorescence can be obtained efficiently. Even if the excitation light has a wavelength of 400 to 419 nm or 501 to 530 nm, the efficiency is lowered, but the ceramic composite for light conversion of the present invention can emit fluorescence. Further, even if the excitation light is near-ultraviolet light having a wavelength of 300 to 360 nm, the ceramic composite for light conversion of the present invention can emit fluorescence.

又，本發明之光轉換用陶瓷複合材料可加工成任意之形狀，但較佳為板狀體。其原因在於，板狀體為可容易地成形加工之形狀，可僅以獲得所期望之色度之發光之方式調整厚度並載置於光器件，而構成轉換光源之光並發光之光器件。 Further, the ceramic composite for light conversion of the present invention can be processed into any shape, but is preferably a plate-like body. The reason for this is that the plate-like body is in a shape that can be easily formed and processed, and the thickness can be adjusted to obtain the light of the desired chromaticity and placed on the optical device, thereby forming an optical device that converts the light of the light source and emits light.

(光轉換用陶瓷複合材料之製造方法) (Manufacturing method of ceramic composite for light conversion)

本發明之光轉換用陶瓷複合材料可藉由如下方式而製造：將原料粉末以獲得所期望之成分比率之光轉換用陶瓷複合材料之比率進行混合，使所獲得之原料混合粉末成形，並進行燒成。 The ceramic composite material for light conversion of the present invention can be produced by mixing raw material powders at a ratio of a ceramic composite material for light conversion to obtain a desired composition ratio, and shaping the obtained raw material mixed powder. Burnt.

作為較佳之製造方法，可採用如下方法：首先，將除成為光轉換用陶瓷複合材料之La源之La源化合物以外的原料粉末混合，對所獲得之混合粉末進行煅燒，而預先製備由Ln3Al5O12：Ce或α-Al2O3所構成之煅燒粉末，此後，以成為本發明之光轉換用陶瓷複合材料之成分之方式向 煅燒粉末添加混合La源化合物，使所獲得之含La混合粉末成形，並進行燒成。根據該方法，即便於較短之燒成時間內，亦可製造本發明之光轉換用陶瓷複合材料。 As a preferable production method, a raw material powder other than the La source compound which is a La source which is a ceramic composite for light conversion is mixed, and the obtained mixed powder is calcined, and previously prepared by Ln 3 a calcined powder composed of Al 5 O 12 :Ce or α-Al 2 O 3 , and thereafter, a La source compound is added to the calcined powder so as to be a component of the ceramic composite for light conversion of the present invention, and the obtained The La mixed powder was molded and fired. According to this method, the ceramic composite for light conversion of the present invention can be produced even in a short firing time.

除La源化合物以外之原料粉末可列舉構成本發明之光轉換用陶瓷複合材料之Al源化合物、Ln源化合物(Ln為選自Y、Lu、及Tb中之至少一種元素)、及Ce源化合物。Al源化合物、Ln源化合物、及Ce源化合物較佳為作為各個金屬元素之氧化物之Al2O3、Ln2O3(Ln為選自Y、Lu、及Tb中之至少一種元素)、及CeO2，但亦可為於混合時並非氧化物而於燒成過程等中容易地變為氧化物之碳酸鹽等化合物。 The raw material powder other than the La source compound may, for example, be an Al source compound or an Ln source compound (Ln is at least one selected from the group consisting of Y, Lu, and Tb) constituting the ceramic composite for light conversion of the present invention, and a Ce source compound. . The Al source compound, the Ln source compound, and the Ce source compound are preferably Al 2 O 3 or Ln 2 O 3 (Ln is at least one element selected from the group consisting of Y, Lu, and Tb) as an oxide of each metal element, And CeO 2 , but it may be a compound such as a carbonate which is easily converted into an oxide in a baking process or the like at the time of mixing.

對於除La源化合物以外之原料粉末之混合方法，並無特別限制，可採用其本身公知之方法，例如可採用如下方法等：進行乾式混合之方法；於在實質上不與原料各成分發生反應之非活性溶劑中進行濕式混合後去除溶劑之方法。作為使用進行濕式混合之方法時之溶劑，通常使用如甲醇、乙醇之醇。作為混合裝置，可較佳地使用V型混合機、滾動式攪拌機、球磨機、振磨機、介質攪拌磨機等。再者，作為同時混合所有原料粉末之情形時的原料粉末之混合方法，亦可較佳地使用相同之方法。 The mixing method of the raw material powder other than the La source compound is not particularly limited, and a method known per se can be employed. For example, the following method or the like can be employed: a method of performing dry mixing; and substantially does not react with each component of the raw material. A method of removing a solvent after performing wet mixing in an inert solvent. As the solvent used in the method of performing wet mixing, an alcohol such as methanol or ethanol is usually used. As the mixing device, a V-type mixer, a rolling type agitator, a ball mill, a vibrating machine, a medium agitating mill, or the like can be preferably used. Further, as a method of mixing the raw material powders in the case where all the raw material powders are simultaneously mixed, the same method can be preferably used.

於預先製備煅燒粉末之情形時，煅燒時之環境並無特別限制，但較佳為大氣環境、非活性環境、或真空環境，煅燒時之溫度為生成由Ln3Al5O12：Ce或α-Al2O3所構成之粉末之溫度，較佳為不過度地推進燒結之溫度。具體而言，煅燒時之溫度較佳為1350~1550℃。只要可實現於上述條件下之熱處理，則對於使用於煅燒之加熱爐並無特別限制。例如，可使用利用高頻感應加熱方式或電阻加熱方式之批次式電爐、旋轉窯、流 動化燒成爐、推板式電爐等。 In the case where the calcined powder is prepared in advance, the environment at the time of calcination is not particularly limited, but is preferably an atmospheric environment, an inactive environment, or a vacuum environment, and the temperature at the time of calcination is generated by Ln 3 Al 5 O 12 :Ce or α. The temperature of the powder composed of -Al 2 O 3 is preferably a temperature at which the sintering is not excessively advanced. Specifically, the temperature at the time of calcination is preferably from 1,350 to 1,550 °C. There is no particular limitation on the heating furnace used for the calcination as long as the heat treatment under the above conditions can be achieved. For example, a batch type electric furnace, a rotary kiln, a fluidized baking furnace, a pusher type electric furnace, or the like using a high frequency induction heating method or a resistance heating method can be used.

於預先製備煅燒粉末之情形時，煅燒粉末亦受原料粉末之粒度分佈或煅燒條件之影響，存在凝集或燒結之情形，因此視需要進行粉碎。對於粉碎方法，並無特別限制，可採用其本身公知之方法，例如可採用如下方法等：乾式粉碎；於在實質上不與煅燒粉末各種成分發生反應之非活性溶劑中進行濕式粉碎後去除溶劑。作為使用進行濕式粉碎之方法時之溶劑，通常使用如甲醇、乙醇之醇。作為粉碎裝置，可較佳地使用輥式破碎機、球磨機、珠磨機、搗碎機等。 In the case where the calcined powder is prepared in advance, the calcined powder is also affected by the particle size distribution or calcination conditions of the raw material powder, and there is a case of agglomeration or sintering, so that pulverization is carried out as needed. The pulverization method is not particularly limited, and a method known per se can be employed. For example, the following method or the like can be employed: dry pulverization; removal after wet pulverization in an inert solvent which does not substantially react with various components of the calcined powder Solvent. As the solvent used in the method of wet pulverization, an alcohol such as methanol or ethanol is usually used. As the pulverizing device, a roll crusher, a ball mill, a bead mill, a masher, or the like can be preferably used.

於預先製備煅燒粉末之情形時，以成為本發明之光轉換用陶瓷複合材料之成分(最終生成物之成分)之方式，向煅燒粉末、或者粉碎煅燒粉末所獲得之粉末追加添加原料粉末之La源化合物，混合該等粉末而製備含La混合粉末。添加之La源化合物只要成為最終生成物之成分，則並無特別限制，但通常相對於煅燒粉末100質量%，以氧化物換算計為1~50質量%，較佳為1~30質量%。此處，所謂氧化物換算，係指將La源化合物換算成La2O3。又，作為La源化合物，較佳為La2O3，但亦可為於混合時並非氧化物而於燒成過程等中容易變為氧化物之碳酸鹽等化合物。又，該情形時之混合方法亦與上述原料粉末之混合方法相同。 When the calcined powder is prepared in advance, the raw material powder is additionally added to the powder obtained by calcining the powder or pulverizing the calcined powder so as to be a component (a component of the final product) of the ceramic composite for light conversion of the present invention. The source compound was mixed to prepare a La-containing mixed powder. The added La source compound is not particularly limited as long as it is a component of the final product, and is usually 1 to 50% by mass, preferably 1 to 30% by mass, based on 100% by mass of the calcined powder. Here, in terms of oxides, La refers to the source compound in terms of La 2 O 3. Further, the La source compound is preferably La 2 O 3 , but may be a compound such as a carbonate which is likely to be an oxide in a firing process or the like during the mixing. Further, the mixing method in this case is also the same as the mixing method of the above raw material powder.

將所有原料粉末混合而獲得之原料混合粉末、或者向由除La源化合物以外之原料粉末製備之煅燒粉末追加添加並混合La源化合物而獲得之含La混合粉末的成形方法並無特別限制，但較佳為壓製成形法、或片成形法、擠壓成形法等。於獲得板狀體之光轉換用陶瓷複合材料之情形時，較佳為採用片成形法之一種即刮刀(doctor blade)法，為了獲得更緻密 之光轉換用陶瓷複合材料，較佳為於片成形後採用壓製成形法之一種即熱均壓壓製等成形法。 The method of forming the La-containing mixed powder obtained by additionally adding and mixing the La source compound to the calcined powder prepared by mixing the raw material powders other than the La source compound is not particularly limited, but It is preferably a press molding method, a sheet molding method, an extrusion molding method, or the like. In the case of obtaining a ceramic composite for light conversion of a plate-like body, it is preferable to use a doctor blade method which is a sheet forming method in order to obtain a denser method. The ceramic composite material for light conversion is preferably a forming method such as hot press pressing which is a press forming method after the sheet is formed.

藉由以上之方法而成形所得之成形體之燒成方法係於由上述任一混合粉末所構成的成形體之情形時均相同，且如下所述。成形體之燒成時之環境並無特別限制，但較佳為大氣環境、非活性環境、或真空環境。燒成時之溫度係只要為形成本發明之光轉換用陶瓷複合材料之構成相之溫度，則並無特別限制，但較佳為1600~1750℃。只要可實現於上述條件下之熱處理，則對於使用於燒成之加熱爐並無特別限制。例如，可使用利用高頻感應加熱方式或電阻加熱方式之批次式電爐、旋轉窯、流動化燒成爐、推板式電爐等。或者，亦可採用同時進行成形及燒成之熱壓法。 The firing method of the molded body obtained by the above method is the same in the case of the molded body composed of any of the above mixed powders, and is as follows. The environment at the time of firing of the formed body is not particularly limited, but is preferably an atmospheric environment, an inactive environment, or a vacuum environment. The temperature at the time of firing is not particularly limited as long as it is the temperature at which the constituent phase of the ceramic composite for light conversion of the present invention is formed, but is preferably 1600 to 1750 °C. The heat treatment used for the firing is not particularly limited as long as the heat treatment under the above conditions can be achieved. For example, a batch type electric furnace, a rotary kiln, a fluidized baking furnace, a pusher type electric furnace, or the like using a high frequency induction heating method or a resistance heating method can be used. Alternatively, a hot pressing method in which molding and firing are simultaneously performed may be employed.

藉由上述方法而燒成所得之光轉換用陶瓷複合材料亦可於非活性氣體環境或還原性氣體環境中進行熱處理。於非活性氣體環境或還原性氣體環境中，在1000~2000℃之溫度範圍內對藉由上述方法而燒成所得之光轉換用陶瓷複合材料進行熱處理，藉此可進一步提高光轉換用陶瓷複合材料之螢光強度。熱處理溫度較佳為1100~1700℃，更佳為1400~1600℃。 The ceramic composite for light conversion obtained by the above-described method can also be heat-treated in an inert gas atmosphere or a reducing gas atmosphere. The ceramic composite for light conversion obtained by the above method is heat-treated in an inert gas atmosphere or a reducing gas atmosphere in a temperature range of 1000 to 2000 ° C, whereby the ceramic composite for light conversion can be further improved. The intensity of the material. The heat treatment temperature is preferably from 1,100 to 1,700 ° C, more preferably from 1,400 to 1,600 ° C.

(發光裝置) (lighting device)

本發明之發光裝置具備發光元件及本發明之光轉換用陶瓷複合材料。發光元件較佳為發出於波長420~500nm具有波峰之光者。其原因在於，藉由該波長，而激發光轉換用陶瓷複合材料之螢光相，獲得螢光。波長進而較佳為於440~480nm具有波峰。其原因在於，螢光相之激發效率較高，可高效率地獲得螢光，對發光裝置之高效率化較佳。作為發光元件，例如可 列舉發光二極體元件、及產生雷射光之元件等，但為了小型且低價，較佳為發光二極體元件。作為發光二極體元件，較佳為藍色發光二極體元件。 The light-emitting device of the present invention comprises a light-emitting element and the ceramic composite material for light conversion of the present invention. Preferably, the light-emitting element emits light having a peak at a wavelength of 420 to 500 nm. This is because the fluorescence phase of the ceramic composite for light conversion is excited by the wavelength to obtain fluorescence. The wavelength is further preferably a peak at 440 to 480 nm. This is because the excitation efficiency of the fluorescent phase is high, and the fluorescence can be efficiently obtained, which is preferable for the efficiency of the light-emitting device. As a light-emitting element, for example Although a light-emitting diode element and an element for generating laser light are cited, in order to be small and inexpensive, a light-emitting diode element is preferable. As the light-emitting diode element, a blue light-emitting diode element is preferable.

光轉換用陶瓷複合材料較佳為發出於540~580nm具有主波長之螢光者，或於含有Gd之情形時為發出於波長560~580nm具有主波長之螢光者。發光裝置較佳為白色發光裝置。 The ceramic composite for light conversion is preferably a phosphor having a dominant wavelength of 540 to 580 nm, or a phosphor having a dominant wavelength of 560 to 580 nm when Gd is contained. The illuminating device is preferably a white illuminating device.

本發明之發光裝置係利用如下之光：將自發光元件發出之光照射至光轉換用陶瓷複合材料，穿透光轉換用陶瓷複合材料之透光相之光；及藉由螢光相而轉換波長之光。 The light-emitting device of the present invention utilizes light that irradiates light emitted from the light-emitting element to the ceramic composite for light conversion, penetrates the light of the light-transmitting phase of the ceramic composite for light conversion, and converts by the fluorescent phase Wave of light.

本發明之發光裝置具備本發明之光轉換用陶瓷複合材料，因此可與藍色發光元件組合而獲得高效率之白色發光裝置。又，本發明之發光裝置具備本發明之光轉換用陶瓷複合材料，因此可調整為白色，且色不均、偏差較小，光轉換用陶瓷複合體材料本身為塊體，無需封入樹脂，因此不會發生因熱、光引起之劣化，而可實現高輸出化、高效率化。 Since the light-emitting device of the present invention includes the ceramic composite for light conversion of the present invention, it can be combined with a blue light-emitting element to obtain a highly efficient white light-emitting device. Moreover, since the light-emitting device of the present invention includes the ceramic composite material for light conversion of the present invention, it can be adjusted to white, and the color unevenness and variation are small, and the ceramic composite material for light conversion itself is a bulk, and it is not necessary to enclose the resin. High-output and high efficiency can be achieved without deterioration due to heat or light.

又，本發明之發光裝置係藉由使用本發明之光轉換用陶瓷複合材料，而標準化光束(轉換效率)良好。可認為，標準化光束(轉換效率)係穿透光轉換用陶瓷複合材料、或經光轉換之光能量相對於發光元件所發出之光能量的比率。本發明之光轉換用陶瓷複合材料係可將發光元件所發出之光能量轉換成黃色光，並且減少不被光轉換而穿透之藍色光之損失，故而具有較高之標準化光束(轉換效率)。 Further, in the light-emitting device of the present invention, the normalized light beam (conversion efficiency) is good by using the ceramic composite for light conversion of the present invention. It is considered that the normalized beam (conversion efficiency) is a ratio of the light-transforming ceramic composite or the light-converted light energy to the light energy emitted from the light-emitting element. The ceramic composite material for light conversion of the present invention can convert the light energy emitted by the light-emitting element into yellow light and reduce the loss of blue light that is not transmitted by the light conversion, thereby having a high normalized light beam (conversion efficiency). .

[實施例] [Examples]

以下，列舉具體例，進一步詳細地對本發明進行說明。首先，對在本發明中所使用之測定方法進行說明。 Hereinafter, the present invention will be described in further detail by way of specific examples. First, the measurement method used in the present invention will be described.

(光轉換用陶瓷複合材料之結晶相之鑑定及定量方法) (Identification and Quantification of Crystal Phase of Ceramic Composites for Optical Conversion)

構成光轉換用陶瓷複合材料之結晶相之鑑定、定量係使用利用CuK α射線之Rigaku公司製造之X射線繞射裝置(Ultima IV Protectus)、及該裝置所附帶之合併粉末X射線解析軟體PDXL而進行。藉由上述X射線繞射裝置而獲得X射線繞射資料，藉由PDXL而鑑定結晶相，進而藉由裏特沃爾德法來對結晶相進行定量。根據該結果，求出各結晶相之質量比率。 The identification and quantification of the crystal phase constituting the ceramic composite for light conversion is performed by using an X-ray diffraction device (Ultima IV Protectus) manufactured by Rigaku Co., Ltd. using CuK α ray, and a combined powder X-ray analysis software PDXL attached to the device. get on. The X-ray diffraction data is obtained by the above X-ray diffraction device, the crystal phase is identified by PDXL, and the crystal phase is quantified by the Ritterwald method. Based on the results, the mass ratio of each crystal phase was determined.

將Ln3Al5O12：Ce作為螢光相，將除Ln3Al5O12：Ce以外之結晶相作為透光相，求出各個相之質量比率，將透光相之LaAl11O18、任意成分之α-Al2O3及LaAlO3之質量比率除以透光相之質量比率，藉此可求出構成透光相之各結晶相相對於透光相之質量比率。 Ln 3 Al 5 O 12 :Ce is used as a fluorescent phase, and a crystal phase other than Ln 3 Al 5 O 12 :Ce is used as a light-transmitting phase, and the mass ratio of each phase is determined, and the light-transmitting phase of LaAl 11 O 18 is obtained. The mass ratio of α-Al 2 O 3 and LaAlO 3 of an arbitrary component is divided by the mass ratio of the light-transmitting phase, whereby the mass ratio of each crystal phase constituting the light-transmitting phase to the light-transmitting phase can be obtained.

又，如下所述般進行Ln3Al5O12：Ce或(Ln,La)3Al5O12：Ce含有Ln、La、及Ce之確認。利用掃描式電子顯微鏡對以成為鏡面狀態之方式研磨而得之本發明之光轉換用陶瓷複合材料的截面之反射電子像進行攝影，並利用該顯微鏡所附帶之EDS(Energy Dispersive Spectroscopy，能量色散光譜)裝置而獲得與上述反射電子像相同視野之各構成元素之元素映射圖。將所獲得之反射電子像與元素映射圖進行對比，確認到Ln3Al5O12：Ce或(Ln,La)3Al5O12：Ce含有Ce、La、或者其他稀土元素。 Further, Ln 3 Al 5 O 12 :Ce or (Ln,La) 3 Al 5 O 12 :Ce was confirmed to contain Ln, La, and Ce as follows. The reflected electron image of the cross section of the ceramic composite for light conversion of the present invention obtained by polishing in a mirror state is imaged by a scanning electron microscope, and EDS (Energy Dispersive Spectroscopy) attached to the microscope is used. The device obtains an element map of each constituent element in the same field of view as the reflected electron image. Comparing the obtained reflected electron image with the element map, it was confirmed that Ln 3 Al 5 O 12 :Ce or (Ln,La) 3 Al 5 O 12 :Ce contains Ce, La, or other rare earth elements.

(光轉換用陶瓷複合材料之螢光特性之評估方法) (Evaluation method of fluorescent characteristics of ceramic composite materials for light conversion)

光轉換用陶瓷複合材料之螢光之主波長、內部量子效率、及最大螢光強度可利用在大塚電子製造之QE-1100組合有積分球之固體量子效率測定裝置而測得、算出。於將光轉換用陶瓷複合材料之一部分加工成16×0.2mm之圓板狀後，安裝至積分球內，使用固體量子效率測定裝置測得激發波長 460nm之激發光光譜及螢光光譜，同時測定內部量子效率。內部量子效率係藉由下述式(1)而算出。 The main wavelength of the fluorescence, the internal quantum efficiency, and the maximum fluorescence intensity of the ceramic composite for light conversion can be measured and calculated using a QE-1100 solid quantum efficiency measuring device in which an integrating sphere is manufactured by Otsuka Electronics Co., Ltd. Processing part of the ceramic composite for light conversion into After a 16×0.2 mm disk shape, it was mounted in an integrating sphere, and the excitation light spectrum and the fluorescence spectrum at an excitation wavelength of 460 nm were measured using a solid quantum efficiency measuring device, and the internal quantum efficiency was measured. The internal quantum efficiency is calculated by the following formula (1).

內部量子效率(%)=(螢光光量子/吸收光量子)×100 (1) Internal quantum efficiency (%) = (fluorescent quantum / absorbed light quantum) × 100 (1)

又，最大螢光強度係導出激發光光譜強度、螢光光譜之460nm時之光譜強度、螢光光譜之螢光峰值波長時之光譜強度，並藉由下述式(2)算出。 Further, the maximum fluorescence intensity is derived from the spectral intensity of the excitation light, the spectral intensity at 460 nm of the fluorescence spectrum, and the spectral intensity at the peak wavelength of the fluorescence spectrum, and is calculated by the following formula (2).

最大螢光強度={螢光光譜之螢光峰值波長之光譜強度/(激發光光譜強度-螢光光譜之460nm時之光譜強度)} (2) Maximum fluorescence intensity = {Spectral intensity of the peak wavelength of the fluorescence spectrum of the fluorescence spectrum / (Spectral intensity of the excitation light spectrum - the spectral intensity at 460 nm of the fluorescence spectrum)} (2)

於本發明中，作為各實施例之光轉換用陶瓷複合材料之相對螢光強度，算出將透光相僅由α-Al2O3構成之比較例之光轉換用陶瓷複合材料之最大螢光強度設為100%的情形時，各實施例之光轉換用陶瓷複合材料之最大螢光強度的相對值。對於Ln為Y之實施例，將把比較例1之光轉換用陶瓷複合材料之最大螢光強度設為100%之情形的相對值作為相對螢光強度，又，對於Ln為Lu之實施例，將把比較例2之光轉換用陶瓷複合材料之最大螢光強度設為100%之情形的相對值作為相對螢光強度。 In the present invention, as the relative fluorescence intensity of the ceramic composite for light conversion of each of the examples, the maximum fluorescence of the ceramic composite for light conversion of a comparative example in which the light-transmitting phase is composed only of α-Al 2 O 3 is calculated. When the intensity is set to 100%, the relative value of the maximum fluorescence intensity of the ceramic composite for light conversion of each of the examples. In the embodiment in which Ln is Y, the relative value of the case where the maximum fluorescence intensity of the ceramic composite for light conversion of Comparative Example 1 is 100% is taken as the relative fluorescence intensity, and in the case where Ln is Lu, The relative value in the case where the maximum fluorescence intensity of the ceramic composite for light conversion of Comparative Example 2 was 100% was taken as the relative fluorescence intensity.

(白色發光二極體之標準化光束) (Standard beam of white light-emitting diode)

使用聚矽氧樹脂將波長轉換構件接合於具有峰值波長455nm之發光色之半導體發光元件上，並利用Spectra-Coop公司製造之總光束測定系統進行測定。標準化光束(轉換效率)係將根據下述式(3)而算出之標準化光束設為轉換效率。 The wavelength conversion member was bonded to a semiconductor light-emitting device having a luminescent color having a peak wavelength of 455 nm using a polyoxyxylene resin, and was measured by a total beam measuring system manufactured by Spectra-Coop. The normalized beam (conversion efficiency) is a conversion efficiency calculated from a normalized beam calculated according to the following formula (3).

(實施例1) (Example 1)

稱量α-Al2O3粉末(純度為99.99%)65.40g、Y2O3粉末(純度為99.9%)34.08g、及CeO2粉末(純度為99.9%)0.52g，將該等原料粉末於乙醇中利用球磨機進行24小時濕式混合後，使用蒸發器對乙醇進行脫介質，從而製備供於煅燒之混合粉末。將所獲得之供於煅燒之混合粉末放入至Al2O3坩鍋，並裝入至批次式電爐，於大氣環境中以1500℃保持3小時進行煅燒，而獲得由Y3Al5O12：Ce及Al2O3所構成之煅燒粉末。煅燒粉末由Y3Al5O12：Ce及Al2O3所構成係藉由X射線繞射分析而確認。 Weighing 65.40 g of α-Al 2 O 3 powder (purity: 99.99%), 34.08 g of Y 2 O 3 powder (purity: 99.9%), and 0.52 g of CeO 2 powder (purity: 99.9%), the raw material powders were weighed. After the wet mixing for 24 hours in a ball mill using ethanol, the ethanol was subjected to de-intermediation using an evaporator to prepare a mixed powder for calcination. The obtained mixed powder for calcination was placed in an Al 2 O 3 crucible, and charged into a batch type electric furnace, and calcined at 1500 ° C for 3 hours in an atmosphere to obtain Y 3 Al 5 O. 12 : a calcined powder composed of Ce and Al 2 O 3 . The calcined powder was composed of Y 3 Al 5 O 12 :Ce and Al 2 O 3 and confirmed by X-ray diffraction analysis.

繼而，向所獲得之煅燒粉末添加相對於煅燒粉末100質量%而為1質量%之La2O3粉末(純度為99.9%)，將該等粉末於乙醇中利用球磨機進行90小時濕式混合後，使用蒸發器對乙醇進行脫介質，從而製備含La混合粉末。相對於所獲得之含La混合粉末100質量份而添加15.75質量份之聚乙烯醇縮丁醛等黏合劑樹脂、2.25質量份之鄰苯二甲酸二丁酯等塑化劑、4質量份之分散劑、135質量份之甲苯等有機溶劑，而製作混合漿料。將所獲得之混合漿料收容至刮刀之漿料收容槽，對可調節漿料收容槽下方之間隙高度之可變式刀片進行調節，使混合漿料自漿料收容槽下方流出為層狀。將所流出之混合漿料以厚度成為50μm左右之方式塗敷至藉由真空吸盤而固定於搬送台之PET膜上，進行乾燥，而製作胚片(greensheet)。將所獲得之胚片以燒成後之厚度成為220~230μm之方式積層6片，利用溫度為85℃、壓力為20MPa之熱均壓壓製進行壓接，而製作積層體。於藉由加熱而可自積層體剝離之發泡剝離片上固定積層體，並以成為特定形狀之方式切斷。利用乾燥機對所切斷之積層體進行加熱，使其自發泡剝離片分 離。使用批次式電爐，將所獲得之積層體於大氣環境下以1700℃保持6小時，進行燒成。以此方式，獲得實施例1之光轉換用陶瓷複合材料。 Then, the calcined powder was added to the obtained calcined powder with respect to 100 mass and after 2 O 3 powder (purity 99.9%), and the like using a ball mill for 90 hours the powder wet-mixed in ethanol and 1% by mass% of La The ethanol was subjected to de-intermediation using an evaporator to prepare a La-containing mixed powder. To the 100 parts by mass of the La-containing mixed powder obtained, 15.75 parts by mass of a binder resin such as polyvinyl butyral, 2.25 parts by mass of a plasticizer such as dibutyl phthalate, and 4 parts by mass of a binder are added. A mixed slurry was prepared by using an organic solvent such as 135 parts by mass of toluene. The obtained mixed slurry is accommodated in the slurry storage tank of the scraper, and the variable insert having a gap height below the slurry storage tank is adjusted, and the mixed slurry flows out from the lower side of the slurry storage tank into a layered shape. The mixed slurry which had flowed out was applied to a PET film fixed to a transfer table by a vacuum chuck so as to have a thickness of about 50 μm, and dried to prepare a green sheet. The obtained green sheets were laminated in such a manner that the thickness after firing was 220 to 230 μm, and pressure bonding was performed by hot press pressing at a temperature of 85 ° C and a pressure of 20 MPa to prepare a laminate. The laminated body is fixed to the foamed release sheet which can be peeled off from the laminate by heating, and is cut so as to have a specific shape. The cut laminate was heated by a dryer to separate the foamed release sheet. The obtained laminate was kept at 1700 ° C for 6 hours in an atmosphere using a batch type electric furnace, and was fired. In this manner, the ceramic composite for light conversion of Example 1 was obtained.

利用上述(光轉換用陶瓷複合材料之結晶相之鑑定及定量方法)中所說明之方法，對構成所獲得之光轉換用陶瓷複合材料之結晶相進行鑑定及定量，並算出各結晶相於透光相中之質量比率。又，利用上述(光轉換用陶瓷複合材料之螢光特性之評估方法)中所說明之方法，測得實施例1之光轉換用陶瓷複合材料之螢光特性。激發光之波長係設為460nm而進行螢光特性評估。根據所獲得之發光光譜算出主波長、內部量子效率、及最大螢光強度。作為相對螢光強度，算出將後述之比較例1之光轉換用陶瓷複合材料之最大螢光強度設為100%之情形時，實施例1之光轉換用陶瓷複合材料之最大螢光強度的相對值。 The crystal phase constituting the obtained ceramic composite for light conversion is identified and quantified by the method described in the above (identification and quantification method of crystal phase of ceramic composite for light conversion), and each crystal phase is calculated. The mass ratio in the optical phase. Moreover, the fluorescence characteristics of the ceramic composite for light conversion of Example 1 were measured by the method described above (method for evaluating the fluorescence characteristics of the ceramic composite for light conversion). Fluorescence characteristics were evaluated by setting the wavelength of the excitation light to 460 nm. The dominant wavelength, the internal quantum efficiency, and the maximum fluorescence intensity were calculated from the obtained luminescence spectrum. When the maximum fluorescence intensity of the ceramic composite for light conversion of Comparative Example 1 to be described later is 100%, the relative fluorescence intensity of the ceramic composite for light conversion of Example 1 is calculated as the relative fluorescence intensity. value.

又，將實施例1之光轉換用陶瓷複合材料用作光轉換構件，而製作白色發光二極體，利用上述(白色發光二極體之標準化光束)中所說明之方法來測定標準化光束(v/Be)。 Moreover, the ceramic composite for light conversion of Example 1 was used as a light conversion member to fabricate a white light-emitting diode, and the normalized light beam was measured by the method described above (normalized beam of white light-emitting diode). v/B e).

於表1中，表示構成實施例1之光轉換用陶瓷複合材料之結晶相及其比率、該光轉換用陶瓷複合材料於以460nm之波長之光激發的情形時之螢光之主波長、內部量子效率及相對螢光強度、以及將實施例1之光轉換用陶瓷複合材料用作光轉換構件之白色發光二極體之標準化光束(v/Be)。實施例1之光轉換用陶瓷複合材料係由Y3Al5O12：Ce、LaAl11O18、及α-Al2O3所構成，透光相中之LaAl11O18相之比率為9.0質量%，透光相中之α-Al2O3相之比率為91.0質量%。未確認到除該等以外之結晶相。又，以460nm之波長之光激發之情形時，實施例1之光轉換用陶瓷複合材料之 主波長為563nm，內部量子效率為71.6%，相對螢光強度為102%，而任一螢光特性之值均顯示高於不含有LaAl11O18之下述比較例1及比較例3~6之值。又，將實施例1之光轉換用陶瓷複合材料應用作光轉換構件之白色發光二極體之標準化光束(v/Be)亦顯示高於比較例1及比較例3~6之值而為0.250。 Table 1 shows the crystal phase and the ratio of the ceramic composite material for light conversion of Example 1, and the main wavelength of the fluorescence when the ceramic composite for light conversion is excited by light having a wavelength of 460 nm. Quantum efficiency and relative fluorescence intensity, and the use of the ceramic composite for light conversion of Example 1 as a normalized light beam of a white light-emitting diode of a light conversion member ( v/B e). The ceramic composite material for light conversion of Example 1 is composed of Y 3 Al 5 O 12 :Ce, LaAl 11 O 18 , and α-Al 2 O 3 , and the ratio of LaAl 11 O 18 phase in the light-transmitting phase is 9.0. The mass%, the ratio of the α-Al 2 O 3 phase in the light-transmitting phase was 91.0% by mass. No crystal phase other than these was confirmed. Further, when excited by light having a wavelength of 460 nm, the ceramic composite for light conversion of Example 1 has a dominant wavelength of 563 nm, an internal quantum efficiency of 71.6%, and a relative fluorescence intensity of 102%, and any of the fluorescent characteristics. The values are all higher than the values of Comparative Example 1 and Comparative Examples 3 to 6 which do not contain LaAl 11 O 18 . Further, the ceramic composite for light conversion of Example 1 is applied as a normalized light beam of a white light-emitting diode of a light conversion member ( v/B e) is also higher than the values of Comparative Example 1 and Comparative Examples 3 to 6 and is 0.250.

(實施例2~7) (Examples 2 to 7)

使添加至藉由與實施例1相同之方法而獲得之煅燒粉末的La2O3粉末相對於煅燒粉末100質量%之質量比率於2~10質量%之範圍內改變，除此之外，以與實施例1相同之方法，獲得實施例2~7之光轉換用陶瓷複合材料。藉由與實施例1相同之方法，對構成所獲得之光轉換用陶瓷複合材料之結晶相進行鑑定及定量，並算出各結晶相於透光相中之質量比率。又，藉由與實施例1相同之方法，測定所獲得之光轉換用陶瓷複合材料於以460nm波長之光激發之情形時的螢光之主波長、內部量子效率、及最大螢光強度。作為相對螢光強度，算出將後述之比較例1之光轉換用陶瓷複合材料之最大螢光強度設為100%的情形時實施例2~7之光轉換用陶瓷複合材料之最大螢光強度的相對值。 The mass ratio of the La 2 O 3 powder added to the calcined powder obtained by the same method as in Example 1 to the mass ratio of 100% by mass of the calcined powder is changed in the range of 2 to 10% by mass, in addition to The ceramic composite for light conversion of Examples 2 to 7 was obtained in the same manner as in Example 1. The crystal phase constituting the obtained ceramic composite for light conversion was identified and quantified by the same method as in Example 1, and the mass ratio of each crystal phase in the light-transmitting phase was calculated. Further, the main wavelength of the fluorescence, the internal quantum efficiency, and the maximum fluorescence intensity when the obtained ceramic material for light conversion was excited by light having a wavelength of 460 nm was measured in the same manner as in Example 1. When the maximum fluorescence intensity of the ceramic composite for light conversion of Comparative Example 1 to be described later is 100%, the maximum fluorescence intensity of the ceramic composite for light conversion of Examples 2 to 7 is calculated as the relative fluorescence intensity. relative value.

又，將實施例2~7之光轉換用陶瓷複合材料用作光轉換構件，與實施例1相同地製作白色發光二極體，測定其標準化光束(v/Be)。 Further, the ceramic composite materials for light conversion of Examples 2 to 7 were used as light-converting members, and a white light-emitting diode was produced in the same manner as in Example 1, and the normalized light beam was measured ( v/B e).

於表1中，表示構成實施例2~7之光轉換用陶瓷複合材料之結晶相及其比率、該光轉換用陶瓷複合材料於以460nm之波長之光激發之情形時的螢光之主波長、內部量子效率及相對螢光強度、以及將實施例2 ~7之光轉換用陶瓷複合材料用作光轉換構件之白色發光二極體之標準化光束(v/Be)。於追加添加至煅燒粉末中之La2O3粉末相對於煅燒粉末100質量%之質量比率至10質量%為止的範圍內，隨著使添加至煅燒粉末中之La2O3粉末之比率變大，而光轉換用陶瓷複合材料之透光相含有之α-Al2O3之比率變小，LaAl11O18之比率變大。伴隨於此，內部量子效率、相對螢光強度、及將實施例2~7之光轉換用陶瓷複合材料應用作光轉換構件之白色發光二極體之標準化光束(v/Be)變大。向煅燒粉末追加添加相對於煅燒粉末100質量%為10質量%之La2O3粉末並進行燒成而獲得的實施例7之光轉換用陶瓷複合材料，係透光相中之LaAl11O18之含有比率成為100質量%，於本發明之含有Y3Al5O12：Ce(於La添加量較多之實施例中，亦存在成為(Y,La)3Al5O12：Ce之情形)作為螢光相之光轉換用陶瓷複合材料中，顯示最大之內部量子效率及相對螢光強度。以460nm之波長之光激發之情形時，實施例7之光轉換用陶瓷複合材料之主波長為561nm，內部量子效率為89.6%，相對螢光強度為130%。又，將實施例6及7之光轉換用陶瓷複合材料應用作光轉換構件之白色發光二極體之標準化光束(v/Be)最大，為0.292。再者，於實施例2~7中之任一實施例中，均未確認到除表1所示之結晶相以外之結晶相。 In Table 1, the crystal phase and the ratio of the ceramic composite materials for light conversion of Examples 2 to 7 and the main wavelength of the fluorescence when the ceramic composite for light conversion is excited by light having a wavelength of 460 nm are shown. , internal quantum efficiency and relative fluorescence intensity, and the use of the ceramic composite for light conversion of Examples 2 to 7 as a normalized light beam of a white light-emitting diode of a light conversion member ( v/B e). In the range of the mass ratio of the La 2 O 3 powder added to the calcined powder to 100% by mass of the calcined powder to 10% by mass, the ratio of the La 2 O 3 powder added to the calcined powder is increased. On the other hand, the ratio of α-Al 2 O 3 contained in the light-transmitting phase of the ceramic composite for light conversion becomes small, and the ratio of LaAl 11 O 18 becomes large. Along with this, the internal quantum efficiency, the relative fluorescence intensity, and the normalized light beam of the white light-emitting diode using the ceramic composite for light conversion of Examples 2 to 7 as a light-converting member ( v/B e) Become bigger. The ceramic composite for light conversion of Example 7 obtained by adding and calcining a La 2 O 3 powder having a content of 10% by mass based on 100% by mass of the calcined powder to the calcined powder is LaAl 11 O 18 in the light-transmitting phase. The content ratio is 100% by mass, and Y 3 Al 5 O 12 :Ce is contained in the present invention. (In the case where the amount of La added is large, there is also a case of (Y, La) 3 Al 5 O 12 : Ce. In the ceramic composite for light conversion of the fluorescent phase, the maximum internal quantum efficiency and relative fluorescence intensity are exhibited. When the light was excited by light having a wavelength of 460 nm, the ceramic composite for light conversion of Example 7 had a dominant wavelength of 561 nm, an internal quantum efficiency of 89.6%, and a relative fluorescence intensity of 130%. Further, the ceramic composite for light conversion of Examples 6 and 7 is applied as a normalized light beam of a white light-emitting diode of a light conversion member ( v/B e) The maximum is 0.292. Further, in any of Examples 2 to 7, no crystal phase other than the crystal phase shown in Table 1 was confirmed.

(實施例8~13) (Examples 8 to 13)

使添加至藉由與實施例1相同之方法而獲得之煅燒粉末中之La2O3粉末相對於煅燒粉末100質量%之質量比率於12.5~30質量%之範圍內改變，除此之外，藉由與實施例1相同之方法而獲得實施例8~13之光轉換用陶瓷複合材料。藉由與實施例1相同之方法，對構成所獲得之光轉換用陶瓷複合 材料之結晶相進行鑑定及定量，並算出各結晶相於透光相中之質量比率。又，藉由與實施例1相同之方法，測定所獲得之光轉換用陶瓷複合材料於以460nm之波長之光激發之情形時的螢光之主波長、內部量子效率、及最大螢光強度。作為相對螢光強度，算出將後述之比較例1之光轉換用陶瓷複合材料之最大螢光強度設為100%之情形時，實施例8~13之光轉換用陶瓷複合材料之最大螢光強度的相對值。 The mass ratio of the La 2 O 3 powder added to the calcined powder obtained by the same method as in Example 1 to 100% by mass of the calcined powder was changed in the range of 12.5 to 30% by mass, in addition to The ceramic composite for light conversion of Examples 8 to 13 was obtained by the same method as in Example 1. The crystal phase constituting the obtained ceramic composite for light conversion was identified and quantified by the same method as in Example 1, and the mass ratio of each crystal phase in the light-transmitting phase was calculated. Further, in the same manner as in Example 1, the main wavelength of the fluorescence, the internal quantum efficiency, and the maximum fluorescence intensity when the obtained ceramic material for light conversion was excited by light having a wavelength of 460 nm was measured. When the maximum fluorescence intensity of the ceramic composite for light conversion of Comparative Example 1 to be described later is set to 100% as the relative fluorescence intensity, the maximum fluorescence intensity of the ceramic composite for light conversion of Examples 8 to 13 is calculated. Relative value.

又，將實施例8~13之光轉換用陶瓷複合材料用作光轉換構件，而與實施例1相同地製作白色發光二極體，測定其標準化光束(v/Be)。 Further, the ceramic composites for light conversion of Examples 8 to 13 were used as light-converting members, and a white light-emitting diode was produced in the same manner as in Example 1, and the normalized light beam was measured ( v/B e).

於表1中，表示構成實施例8~13之光轉換用陶瓷複合材料之結晶相及其比率、該光轉換用陶瓷複合材料於以460nm之波長之光激發之情形時的螢光之主波長、內部量子效率及相對螢光強度、以及將實施例8~13之光轉換用陶瓷複合材料用作光轉換構件之白色發光二極體之標準化光束(v/Be)。使追加添加至煅燒粉末中之La2O3粉末相對於煅燒粉末100質量%之質量比率變大至12.5質量%的實施例8中，生成LaAlO3。藉此，於使添加至煅燒粉末中之La2O3粉末之比率變大至30質量%為止之範圍中，隨著使La2O3粉末之質量比率變大，而含有於透光相中之LaAlO3之比率變大，LaAl11O18相之比率變小。隨著LaAlO3之比率變大，而內部量子效率、相對螢光強度、及白色發光二極體之標準化光束(v/Be)變小，但透光相中之LaAlO3之比率最大之實施例13的光轉換用陶瓷複合材料係主波長為562nm、內部量子效率為65.9%、相對螢光強度為107%，而亦顯示高於不含有LaAl11O18之下述比較例1之值。又，將實施例13之光轉換用陶瓷複合 材料應用作光轉換構件之白色發光二極體之標準化光束(v/Be)顯示高於下述比較例1之值而為0.253。再者，於實施例8~13中之任一實施例中，均未確認到除表1所示之結晶相以外之結晶相。 In Table 1, the crystal phase and the ratio of the ceramic composite materials for light conversion of Examples 8 to 13 and the main wavelength of the fluorescent light when the ceramic composite for light conversion is excited by light having a wavelength of 460 nm are shown. , internal quantum efficiency and relative fluorescence intensity, and the ceramic composite materials for light conversion of Examples 8 to 13 are used as the normalized light beam of the white light-emitting diode of the light conversion member ( v/B e). In Example 8 in which the mass ratio of the La 2 O 3 powder additionally added to the calcined powder to 100% by mass of the calcined powder was increased to 12.5% by mass, LaAlO 3 was formed . In this way, in the range in which the ratio of the La 2 O 3 powder added to the calcined powder is increased to 30% by mass, the mass ratio of the La 2 O 3 powder is increased, and it is contained in the light-transmitting phase. The ratio of LaAlO 3 becomes large, and the ratio of the LaAl 11 O 18 phase becomes small. As the ratio of LaAlO 3 becomes larger, the internal quantum efficiency, relative fluorescence intensity, and the normalized beam of the white light-emitting diode ( v/B e) the ceramic composite for light conversion of Example 13 having a smaller ratio of LaAlO 3 in the light-transmitting phase, having a dominant wavelength of 562 nm, an internal quantum efficiency of 65.9%, and a relative fluorescence intensity of 107%. The value of the following Comparative Example 1 which does not contain LaAl 11 O 18 is shown. Further, the ceramic composite for light conversion of Example 13 is applied as a normalized light beam of a white light-emitting diode of a light conversion member ( v/B e) shows a value higher than the value of Comparative Example 1 described below and is 0.253. Further, in any of Examples 8 to 13, no crystal phase other than the crystal phase shown in Table 1 was confirmed.

(比較例1) (Comparative Example 1)

不向藉由與實施例1相同之方法而獲得之煅燒粉末追加添加La2O3粉末，而僅使煅燒粉末成形，除此之外，藉由與實施例1相同之方法而獲得比較例1之光轉換用陶瓷複合材料。藉由與實施例1相同之方法，對構成所獲得之光轉換用陶瓷複合材料之結晶相進行鑑定及定量，並算出各結晶相於透光相中之質量比率。又，藉由與實施例1相同之方法，測定所獲得之光轉換用陶瓷複合材料於以460nm之波長之光激發之情形時的螢光之主波長、內部量子效率、及最大螢光強度。 Not to the calcined powder by the same procedures as Example 1 to obtain the powder was added over 2 O 3 La, and only the calcined powder formed, except by the same procedures as Example 1 Comparative Example 1 was obtained Ceramic composite material for light conversion. The crystal phase constituting the obtained ceramic composite for light conversion was identified and quantified by the same method as in Example 1, and the mass ratio of each crystal phase in the light-transmitting phase was calculated. Further, in the same manner as in Example 1, the main wavelength of the fluorescence, the internal quantum efficiency, and the maximum fluorescence intensity when the obtained ceramic material for light conversion was excited by light having a wavelength of 460 nm was measured.

又，將比較例1之光轉換用陶瓷複合材料用作光轉換構件，而與實施例1相同地製作白色發光二極體，測定其標準化光束(v/Be)。 Further, the ceramic composite for light conversion of Comparative Example 1 was used as a light conversion member, and a white light-emitting diode was produced in the same manner as in Example 1, and the normalized light beam was measured ( v/B e).

於表1中，表示構成比較例1之光轉換用陶瓷複合材料之結晶相及其比率、該光轉換用陶瓷複合材料於以460nm波長之光激發之情形時的螢光之主波長、內部量子效率及相對螢光強度、以及將比較例1之光轉換用陶瓷複合材料用作光轉換構件之白色發光二極體之標準化光束(v/Be)。比較例1之光轉換用陶瓷複合材料僅由Y3Al5O12：Ce及α-Al2O3構成，透光相僅由α-Al2O3構成。又，以460nm波長之光激發之情形時，比較例1之光轉換用陶瓷複合材料之主波長為563nm，內部量子效率為64.1%。將把比較例1之光轉換用陶瓷複合材料之最大螢光強度設為100%情形時實施例1~13之光轉換用陶瓷複合材料之最大螢光強度的相對值設 為相對螢光強度。又，將比較例1之光轉換用陶瓷複合材料應用作光轉換構件之白色發光二極體之標準化光束(v/Be)為0.234。 Table 1 shows the crystal phase and the ratio of the ceramic composite material for light conversion of Comparative Example 1, and the main wavelength of the fluorescence and the internal quantum of the ceramic composite for light conversion when excited by light having a wavelength of 460 nm. Efficiency and relative fluorescence intensity, and the ceramic composite material for light conversion of Comparative Example 1 is used as a normalized light beam of a white light-emitting diode of a light conversion member ( v/B e). The ceramic composite for light conversion of Comparative Example 1 was composed only of Y 3 Al 5 O 12 :Ce and α-Al 2 O 3 , and the light-transmitting phase was composed only of α-Al 2 O 3 . Further, when excited by light having a wavelength of 460 nm, the main wavelength of the ceramic composite for light conversion of Comparative Example 1 was 563 nm, and the internal quantum efficiency was 64.1%. When the maximum fluorescence intensity of the ceramic composite for light conversion of Comparative Example 1 was 100%, the relative value of the maximum fluorescence intensity of the ceramic composite for light conversion of Examples 1 to 13 was set as the relative fluorescence intensity. Further, the ceramic composite for light conversion of Comparative Example 1 was applied as a normalized light beam of a white light-emitting diode of a light conversion member ( v/B e) is 0.234.

(實施例14) (Example 14)

稱量α-Al2O3粉末(純度為99.99%)53.89g、Lu2O3粉末(純度為99.9%)45.71g、及CeO2粉末(純度為99.9%)0.40g而作為原料，除此之外，藉由與實施例1相同之方法而獲得由Lu3Al5O12：Ce及Al2O3所構成之煅燒粉末。與實施例1相同地，煅燒粉末由Lu3Al5O12：Ce及Al2O3所構成係藉由X射線繞射分析而確認。與實施例1相同地，向所獲得之煅燒粉末添加混合相對於煅燒粉末100質量%而為1質量%之La2O3粉末(純度為99.9%)，並進行成形、燒成，而獲得實施例14之光轉換用陶瓷複合材料。藉由與實施例1相同之方法，對構成所獲得之光轉換用陶瓷複合材料之結晶相進行鑑定及定量，並算出各結晶相於透光相中之質量比率。又，藉由與實施例1相同之方法，測定所獲得之光轉換用陶瓷複合材料於以460nm之波長之光激發之情形時的螢光之主波長、內部量子效率、及最大螢光強度。作為相對螢光強度，算出將後述之比較例2之光轉換用陶瓷複合材料之最大螢光強度設為100%的情形時實施例14之光轉換用陶瓷複合材料之最大螢光強度的相對值。 Weighed 53.89 g of α-Al 2 O 3 powder (purity: 99.99%), 45.71 g of Lu 2 O 3 powder (purity: 99.9%), and 0.40 g of CeO 2 powder (purity: 99.9%) as a raw material. A calcined powder composed of Lu 3 Al 5 O 12 :Ce and Al 2 O 3 was obtained by the same method as in Example 1. In the same manner as in Example 1, the calcined powder was composed of Lu 3 Al 5 O 12 :Ce and Al 2 O 3 and confirmed by X-ray diffraction analysis. In the same manner as in Example 1, a La 2 O 3 powder (purity: 99.9%) which was mixed with 100% by mass of the calcined powder and 1% by mass was added to the obtained calcined powder, and was molded and calcined to obtain a calcined powder. Example 14 is a ceramic composite for light conversion. The crystal phase constituting the obtained ceramic composite for light conversion was identified and quantified by the same method as in Example 1, and the mass ratio of each crystal phase in the light-transmitting phase was calculated. Further, in the same manner as in Example 1, the main wavelength of the fluorescence, the internal quantum efficiency, and the maximum fluorescence intensity when the obtained ceramic material for light conversion was excited by light having a wavelength of 460 nm was measured. The relative fluorescence intensity is calculated as the relative fluorescence intensity of the ceramic composite for light conversion of Example 14 when the maximum fluorescence intensity of the ceramic composite for light conversion of Comparative Example 2 to be described later is 100%. .

又，將實施例14之光轉換用陶瓷複合材料用作光轉換構件，而與實施例1相同地製作白色發光二極體，測定其標準化光束(v/Be)。 Further, the ceramic composite for light conversion of Example 14 was used as a light-converting member, and a white light-emitting diode was produced in the same manner as in Example 1, and the normalized light beam was measured ( v/B e).

於表2中，表示構成實施例14之光轉換用陶瓷複合材料之結晶相及其比率、該光轉換用陶瓷複合材料於以460nm波長之光激發之情 形時的螢光之主波長、內部量子效率及相對螢光強度、以及將實施例14之光轉換用陶瓷複合材料用作光轉換構件之白色發光二極體之標準化光束(v/Be)。實施例14之光轉換用陶瓷複合材料由Lu3Al5O12：Ce、LaAl11O18、及α-Al2O3所構成，透光相中之LaAl11O18相之比率為15.0質量%，透光相中之α-Al2O3相之比率為85.0質量%。未確認到除該等以外之結晶相。又，以460nm波長之光激發之情形時，實施例14之光轉換用陶瓷複合材料之主波長為547nm、內部量子效率為79.3%、相對螢光強度為109%，而顯示高於不含有LaAl11O18之下述比較例2之值。又，將實施例14之光轉換用陶瓷複合材料應用作光轉換構件之白色發光二極體之標準化光束(v/Be)顯示高於比較例2之值而為0.254。 In Table 2, the crystal phase and the ratio of the ceramic composite material for light conversion of Example 14 and the main wavelength of the fluorescence when the ceramic composite for light conversion is excited by light having a wavelength of 460 nm are shown. Efficiency and relative fluorescence intensity, and the use of the ceramic composite for light conversion of Example 14 as a normalized light beam of a white light-emitting diode of a light conversion member ( v/B e). The ceramic composite for light conversion of Example 14 is composed of Lu 3 Al 5 O 12 :Ce, LaAl 11 O 18 , and α-Al 2 O 3 , and the ratio of the LaAl 11 O 18 phase in the light-transmitting phase is 15.0 mass. %, the ratio of the α-Al 2 O 3 phase in the light-transmitting phase was 85.0% by mass. No crystal phase other than these was confirmed. Further, when excited by light having a wavelength of 460 nm, the ceramic composite for light conversion of Example 14 had a dominant wavelength of 547 nm, an internal quantum efficiency of 79.3%, and a relative fluorescence intensity of 109%, which was higher than that of LaAl-free. the following 11 O 18 Comparative Example 2 of the value. Further, the ceramic composite for light conversion of Example 14 is applied as a normalized light beam of a white light-emitting diode of a light conversion member ( v/B e) shows a value higher than that of Comparative Example 2 and is 0.254.

(實施例5~21) (Examples 5 to 21)

使添加至藉由與實施例14相同之方法而獲得之煅燒粉末中的La2O3粉末相對於煅燒粉末100質量%之質量比率於2~12.5質量%之範圍內改變，除此之外，藉由與實施例14相同之方法而獲得實施例15~21之光轉換用陶瓷複合材料。藉由與實施例1相同之方法，對構成所獲得之光轉換用陶瓷複合材料之結晶相進行鑑定及定量，並算出各結晶相於透光相中之質量比率。又，藉由與實施例1相同之方法，測定所獲得之光轉換用陶瓷複合材料於以460nm波長之光激發之情形時的螢光之主波長、內部量子效率、及最大螢光強度。作為相對螢光強度，算出將後述之比較例2之光轉換用陶瓷複合材料之最大螢光強度設為100%的情形時實施例15~21之光轉換用陶瓷複合材料之最大螢光強度的相對值。 The mass ratio of the La 2 O 3 powder added to the calcined powder obtained by the same method as in Example 14 to 100% by mass of the calcined powder was changed in the range of 2 to 12.5% by mass, in addition to The ceramic composite for light conversion of Examples 15 to 21 was obtained by the same method as that of Example 14. The crystal phase constituting the obtained ceramic composite for light conversion was identified and quantified by the same method as in Example 1, and the mass ratio of each crystal phase in the light-transmitting phase was calculated. Further, the main wavelength of the fluorescence, the internal quantum efficiency, and the maximum fluorescence intensity when the obtained ceramic material for light conversion was excited by light having a wavelength of 460 nm was measured in the same manner as in Example 1. When the maximum fluorescence intensity of the ceramic composite for light conversion of Comparative Example 2 to be described later is 100%, the maximum fluorescence intensity of the ceramic composite for light conversion of Examples 15 to 21 is calculated as the relative fluorescence intensity. relative value.

又，將實施例15~21之光轉換用陶瓷複合材料用作光轉換 構件，而與實施1相同地製作白色發光二極體，測定其標準化光束(v/Be)。 Further, the ceramic composites for light conversion of Examples 15 to 21 were used as light-converting members, and a white light-emitting diode was produced in the same manner as in the first embodiment, and the normalized light beam was measured ( v/B e).

於表2中，表示構成實施例15~21之光轉換用陶瓷複合材料之結晶相及其比率、該光轉換用陶瓷複合材料於以460nm波長之光激發之情形時的螢光之主波長、內部量子效率及相對螢光強度、以及將實施例15~21之光轉換用陶瓷複合材料用作光轉換構件之白色發光二極體之標準化光束(v/Be)。於追加添加至煅燒粉末中之La2O3粉末相對於煅燒粉末100質量%之質量比率至12.5質量%為止的範圍內，隨著使添加至煅燒粉末中之La2O3粉末之比率變大，而光轉換用陶瓷複合材料之透光相含有之α-Al2O3之比率變小，LaAl11O18之比率變大。伴隨於此，內部量子效率、相對螢光強度、及白色發光二極體之標準化光束(v/Be)變大。向煅燒粉末追加添加相對於煅燒粉末100質量%而為12.5質量%之La2O3粉末並進行燒成而獲得的實施例21之光轉換用陶瓷複合材料係透光相中之LaAl11O18之含有比率成為100質量%，於本發明之含有Lu3Al5O12：Ce(於La添加量較多之實施例中，亦存在成為(Lu,La)3Al5O12：Ce之情形)作為螢光相之光轉換用陶瓷複合材料中，顯示最大之內部量子效率及相對螢光強度。以460nm波長之光激發之情形時，實施例21之光轉換用陶瓷複合材料之主波長為544nm，內部量子效率為90.0%，相對螢光強度為131%。又，將實施例21之光轉換用陶瓷複合材料應用作光轉換構件之白色發光二極體之標準化光束(v/Be)最大，為0.294。再者，於實施例15~21中之任一實施例中，均未確認到除表2所示之結晶相以外之結晶相。 In Table 2, the crystal phase and the ratio of the ceramic composite for light conversion of Examples 15 to 21, and the main wavelength of the fluorescence when the ceramic composite for light conversion is excited by light having a wavelength of 460 nm, Internal quantum efficiency and relative fluorescence intensity, and the ceramic composite material for light conversion of Examples 15 to 21 is used as a normalized light beam of a white light-emitting diode of a light conversion member ( v/B e). In the range of the mass ratio of the La 2 O 3 powder added to the calcined powder to 100% by mass of the calcined powder to 12.5% by mass, the ratio of the La 2 O 3 powder added to the calcined powder is increased. On the other hand, the ratio of α-Al 2 O 3 contained in the light-transmitting phase of the ceramic composite for light conversion becomes small, and the ratio of LaAl 11 O 18 becomes large. Along with this, the internal quantum efficiency, the relative fluorescence intensity, and the normalized beam of the white light-emitting diode ( v/B e) Become bigger. LaAl 11 O 18 in the light-transmissive phase of the ceramic composite for light conversion of Example 21 obtained by adding and adding a La 2 O 3 powder having a mass ratio of 12.5 mass% to 100% by mass of the calcined powder and calcining the calcined powder The content ratio is 100% by mass, and Lu 3 Al 5 O 12 :Ce is contained in the present invention. (In the case where the amount of La added is large, there is also a case of (Lu,La) 3 Al 5 O 12 :Ce. In the ceramic composite for light conversion of the fluorescent phase, the maximum internal quantum efficiency and relative fluorescence intensity are exhibited. When excited by light having a wavelength of 460 nm, the ceramic composite for light conversion of Example 21 had a dominant wavelength of 544 nm, an internal quantum efficiency of 90.0%, and a relative fluorescence intensity of 131%. Further, the ceramic composite for light conversion of Example 21 is applied as a normalized light beam of a white light-emitting diode of a light conversion member ( v/B e) The maximum is 0.294. Further, in any of Examples 15 to 21, no crystal phase other than the crystal phase shown in Table 2 was observed.

於圖1中，表示利用掃描式電子顯微鏡(日本電子(股)製 造之JSM-6510型)對實施例18、21、及後述之比較例2之光轉換用陶瓷複合材料之表面進行攝影而獲得的SEM照片。使用圖1之SEM照片，利用圖像解析軟體(Mountech(股)製造之Mac-View Ver.4)而求出等效圓直徑。將其結果示於表4。可知，與比較例2之0.83μm相比，實施例18、21粒徑變大為1.40μm、3.0μm。 In Fig. 1, it is shown by a scanning electron microscope (Japan Electronics Co., Ltd.) JSM-6510 type) SEM photograph obtained by photographing the surfaces of the ceramic composites for light conversion of Examples 18 and 21 and Comparative Example 2 to be described later. The equivalent circle diameter was obtained by using an image analysis software (Mac-View Ver. 4 manufactured by Mountech Co., Ltd.) using the SEM photograph of Fig. 1 . The results are shown in Table 4. The particle diameters of Examples 18 and 21 were increased to 1.40 μm and 3.0 μm as compared with 0.83 μm of Comparative Example 2.

(實施例22~26) (Examples 22 to 26)

使添加至藉由與實施例14相同之方法而獲得之煅燒粉末中的La2O3粉末相對於煅燒粉末100質量%之質量比率於15~30質量%之範圍內改變，除此之外，藉由與實施例14相同之方法而獲得實施例22~26之光轉換用陶瓷複合材料。藉由與實施例1相同之方法，得到構成所獲得之光轉換用陶瓷複合材料之結晶相及其比率、該光轉換用陶瓷複合材料於以460nm波長之光激發之情形時的螢光之主波長、內部量子效率、及最大螢光強度。作為相對螢光強度，算出將後述之比較例2之光轉換用陶瓷複合材料之最大螢光強度設為100%的情形時，實施例22~26之光轉換用陶瓷複合材料之最大螢光強度的相對值。 The mass ratio of the La 2 O 3 powder added to the calcined powder obtained by the same method as in Example 14 to 100% by mass of the calcined powder was changed within the range of 15 to 30% by mass, in addition to The ceramic composite for light conversion of Examples 22 to 26 was obtained by the same method as that of Example 14. By the same method as in Example 1, the crystal phase and the ratio of the obtained ceramic composition for light conversion obtained, and the ratio of the ratio of the crystal composite material for the light-converting ceramic composite material excited by light having a wavelength of 460 nm were obtained. Wavelength, internal quantum efficiency, and maximum fluorescence intensity. When the maximum fluorescence intensity of the ceramic composite for light conversion of Comparative Example 2 to be described later is set to 100% as the relative fluorescence intensity, the maximum fluorescence intensity of the ceramic composite for light conversion of Examples 22 to 26 is calculated. Relative value.

又，將實施例22~26之光轉換用陶瓷複合材料用作光轉換構件，而與實施例1相同地製作白色發光二極體，測定其標準化光束(v/Be)。 Further, the ceramic composites for light conversion of Examples 22 to 26 were used as light-converting members, and a white light-emitting diode was produced in the same manner as in Example 1, and the normalized light beam was measured ( v/B e).

於表2中，表示構成實施例22~26之光轉換用陶瓷複合材料之結晶相及其比率、該光轉換用陶瓷複合材料於以460nm波長之光激發之情形時的螢光之主波長、內部量子效率及相對螢光強度、以及將實施例22~26之光轉換用陶瓷複合材料用作光轉換構件之白色發光二極體之標準 化光束(v/Be)。使追加添加至煅燒粉末中之La2O3粉末相對於煅燒粉末100質量%之質量比率變大至15質量%為止的實施例22中，生成LaAlO3。藉此，於使添加至煅燒粉末中之La2O3粉末之比率變大至30質量%為止之範圍內，隨著使La2O3粉末之質量比率變大，而透光相含有之LaAlO3之比率變大，LaAl11O18相之比率變小。隨著LaAlO3之比率變大，而內部量子效率、相對螢光強度、及白色發光二極體之標準化光束(v/Be)變小，透光相中之LaAlO3之比率最大之實施例26之光轉換用陶瓷複合材料係主波長為545nm、內部量子效率為72.2%、相對螢光強度為108%，而亦顯示高於不含有LaAl11O18之下述比較例2之值。又，將實施例26之光轉換用陶瓷複合材料應用作光轉換構件之白色發光二極體的標準化光束(v/Be)顯示高於下述比較例2之值而為0.243。再者，於實施例22~26中之任一實施例中，均未確認到除表1所示之結晶相以外之結晶相。 In Table 2, the crystal phase and the ratio of the ceramic composite material for light conversion of Examples 22 to 26, and the main wavelength of the fluorescence when the ceramic composite for light conversion is excited by light having a wavelength of 460 nm, The internal quantum efficiency and the relative fluorescence intensity, and the ceramic composite for light conversion of Examples 22 to 26 are used as the normalized light beam of the white light-emitting diode of the light conversion member ( v/B e). In Example 22 in which the mass ratio of the La 2 O 3 powder additionally added to the calcined powder to 100% by mass of the calcined powder was increased to 15% by mass, LaAlO 3 was produced. Whereby, in so added to the calcined powder of La 2 O 3 ratio of the powder becomes large up to the range of 30 mass%, so that as the mass ratio of La 2 O 3 powder becomes larger, the light transmittance of the phase containing LaAlO The ratio of 3 becomes larger, and the ratio of the LaAl 11 O 18 phase becomes smaller. As the ratio of LaAlO 3 becomes larger, the internal quantum efficiency, relative fluorescence intensity, and the normalized beam of the white light-emitting diode ( v/B e) The glass composite for light conversion of Example 26 having the largest ratio of LaAlO 3 in the light-transmitting phase has a dominant wavelength of 545 nm, an internal quantum efficiency of 72.2%, and a relative fluorescence intensity of 108%, and also shows It is higher than the value of Comparative Example 2 which does not contain LaAl 11 O 18 . Further, the ceramic composite for light conversion of Example 26 is applied as a normalized light beam of a white light-emitting diode of a light conversion member ( v/B e) shows a value higher than the value of Comparative Example 2 described below and is 0.243. Further, in any of Examples 22 to 26, no crystal phase other than the crystal phase shown in Table 1 was observed.

(比較例2) (Comparative Example 2)

不向藉由與實施例14相同之方法而獲得之煅燒粉末追加添加La2O3粉末，而僅使煅燒粉末成形，除此之外，藉由與實施例14相同之方法而獲得比較例2之光轉換用陶瓷複合材料。藉由與實施例1相同之方法，對構成所獲得之光轉換用陶瓷複合材料之結晶相進行鑑定及定量，並算出各結晶相於透光相中之質量比率。又，藉由與實施例1相同之方法，測定所獲得之光轉換用陶瓷複合材料於以460nm波長之光激發之情形時的螢光之主波長、內部量子效率、及最大螢光強度。 Comparative Example 2 was obtained by the same method as in Example 14 except that the calcined powder obtained by the same method as in Example 14 was additionally added with La 2 O 3 powder, and only the calcined powder was molded. Ceramic composite material for light conversion. The crystal phase constituting the obtained ceramic composite for light conversion was identified and quantified by the same method as in Example 1, and the mass ratio of each crystal phase in the light-transmitting phase was calculated. Further, the main wavelength of the fluorescence, the internal quantum efficiency, and the maximum fluorescence intensity when the obtained ceramic material for light conversion was excited by light having a wavelength of 460 nm was measured in the same manner as in Example 1.

又，將比較例2之光轉換用陶瓷複合材料用作光轉換構件，而與實施例1相同地製作白色發光二極體，測定其標準化光束(v/Be)。 Further, the ceramic composite for light conversion of Comparative Example 2 was used as a light-converting member, and a white light-emitting diode was produced in the same manner as in Example 1, and the normalized light beam was measured ( v/B e).

於表2中，表示構成比較例2之光轉換用陶瓷複合材料之結晶相及其比率、該光轉換用陶瓷複合材料於以460nm波長之光激發之情形時的螢光之主波長、內部量子效率及相對螢光強度、以及將比較例2之光轉換用陶瓷複合材料用作光轉換構件之白色發光二極體之標準化光束(v/Be)。比較例2之光轉換用陶瓷複合材料僅由Lu3Al5O12：Ce及α-Al2O3構成，透光相僅由α-Al2O3構成。又，以460nm波長之光激發之情形時，比較例2之光轉換用陶瓷複合材料之主波長為548nm，內部量子效率為70.8%。又，將把比較例2之光轉換用陶瓷複合材料之最大螢光強度設為100%之情形時，實施例14~26之光轉換用陶瓷複合材料之最大螢光強度的相對值設為相對螢光強度。又，將比較例2之光轉換用陶瓷複合材料應用作光轉換構件之白色發光二極體之標準化光束(v/Be)為0.225。 In Table 2, the crystal phase and the ratio of the ceramic composite material for light conversion of Comparative Example 2, and the main wavelength of the fluorescence, the internal quantum of the ceramic composite for light conversion when excited by light having a wavelength of 460 nm are shown. Efficiency and relative fluorescence intensity, and the ceramic composite material for light conversion of Comparative Example 2 is used as a normalized light beam of a white light-emitting diode of a light conversion member ( v/B e). The ceramic composite for light conversion of Comparative Example 2 was composed only of Lu 3 Al 5 O 12 :Ce and α-Al 2 O 3 , and the light-transmitting phase was composed only of α-Al 2 O 3 . Further, in the case of excitation with light having a wavelength of 460 nm, the main wavelength of the ceramic composite for light conversion of Comparative Example 2 was 548 nm, and the internal quantum efficiency was 70.8%. When the maximum fluorescence intensity of the ceramic composite for light conversion of Comparative Example 2 is 100%, the relative fluorescence intensity of the ceramic composite for light conversion of Examples 14 to 26 is relatively Fluorescence intensity. Further, the ceramic composite for light conversion of Comparative Example 2 was applied as a normalized light beam of a white light-emitting diode of a light conversion member ( v/B e) is 0.225.

(比較例3~6) (Comparative examples 3 to 6)

將添加至藉由與實施例1相同之方法而獲得之煅燒粉末中的粉末自La2O3粉末變更為表3所示之含M化合物粉末，並將其比率設為如表3所示，除此之外，藉由與實施例1相同之方法而獲得比較例3~6之光轉換用陶瓷複合材料。藉由與實施例1相同之方法，對構成所獲得之光轉換用陶瓷複合材料之結晶相進行鑑定及定量，並算出各結晶相於透光相中之質量比率。又，藉由與實施例1相同之方法，測定所獲得之光轉換用陶瓷複合材料於以460nm波長之光激發之情形時的螢光之主波長、內部量子效率、及最大螢光強度。 The powder added to the calcined powder obtained by the same method as in Example 1 was changed from the La 2 O 3 powder to the M-containing compound powder shown in Table 3, and the ratio thereof was set as shown in Table 3. Otherwise, the ceramic composite for light conversion of Comparative Examples 3 to 6 was obtained by the same method as in Example 1. The crystal phase constituting the obtained ceramic composite for light conversion was identified and quantified by the same method as in Example 1, and the mass ratio of each crystal phase in the light-transmitting phase was calculated. Further, the main wavelength of the fluorescence, the internal quantum efficiency, and the maximum fluorescence intensity when the obtained ceramic material for light conversion was excited by light having a wavelength of 460 nm was measured in the same manner as in Example 1.

又，將比較例3~6之光轉換用陶瓷複合材料用作光轉換構件，而與實施例1相同地製作白色發光二極體，測定其標準化光束(v/ Be)。 Further, the ceramic composites for light conversion of Comparative Examples 3 to 6 were used as light-converting members, and a white light-emitting diode was produced in the same manner as in Example 1, and the normalized light beam was measured ( v/ B e).

於表3中，表示構成比較例3~6之光轉換用陶瓷複合材料之結晶相及其比率、該光轉換用陶瓷複合材料於以460nm波長之光激發之情形時的螢光之主波長、內部量子效率及相對螢光強度、以及將比較例3~6之光轉換用陶瓷複合材料用作光轉換構件之白色發光二極體之標準化光束(v/Be)。比較例3~6之光轉換用陶瓷複合材料僅由Y3Al5O12：Ce、MxAlyOz(自比較例3起依次為CeAl11O18、CaAl12O19、SrAl12O19、BaAl12O19)、及α-Al2O3構成，透光相由MxAlyOz及α-Al2O3構成。以460nm波長之光激發之情形時，比較例3、5及6之光轉換用陶瓷複合材料顯示相對較高之最大螢光強度，但內部量子效率均較低，將該等光轉換用陶瓷複合材料應用作光轉換構件之白色發光二極體之標準化光束(v/Be)亦為低於實施例1~13之值。又，比較例4之光轉換用陶瓷複合材料係內部量子效率、最大螢光強度均較低，將該光轉換用陶瓷複合材料應用作光轉換構件之白色發光二極體之標準化光束(v/Be)亦為低於實施例1~13之值。將把比較例1之光轉換用陶瓷複合材料之最大螢光強度設為100%之情形時比較例3~6之光轉換用陶瓷複合材料之最大螢光強度的相對值設為相對螢光強度。 In Table 3, the crystal phase and the ratio of the ceramic composite for light conversion of Comparative Examples 3 to 6 and the main wavelength of the fluorescence when the ceramic composite for light conversion is excited by light having a wavelength of 460 nm are shown. The internal quantum efficiency and the relative fluorescence intensity, and the ceramic composite for light conversion of Comparative Examples 3 to 6 are used as the normalized light beam of the white light-emitting diode of the light conversion member ( v/B e). The ceramic composite for light conversion of Comparative Examples 3 to 6 consisted only of Y 3 Al 5 O 12 :Ce, M x Al y O z (CeAl 11 O 18 , CaAl 12 O 19 , SrAl 12 O in order from Comparative Example 3) 19 , BaAl 12 O 19 ), and α-Al 2 O 3 , the light transmissive phase is composed of M x Al y O z and α-Al 2 O 3 . When the light is excited by light having a wavelength of 460 nm, the ceramic composite materials for light conversion of Comparative Examples 3, 5 and 6 exhibit relatively high maximum fluorescence intensity, but the internal quantum efficiency is low, and the ceramic composite for the light conversion is used. The material is applied as a normalized beam of a white light-emitting diode of a light conversion member ( v/B e) is also lower than the values of Examples 1-13. Further, in the ceramic composite material for light conversion of Comparative Example 4, the internal quantum efficiency and the maximum fluorescence intensity were low, and the ceramic composite material for light conversion was applied as a normalized light beam of a white light-emitting diode of a light conversion member ( v/B e) is also lower than the values of Examples 1-13. When the maximum fluorescence intensity of the ceramic composite for light conversion of Comparative Example 1 is 100%, the relative value of the maximum fluorescence intensity of the ceramic composite for light conversion of Comparative Examples 3 to 6 is set as the relative fluorescence intensity. .

(實施例27~34) (Examples 27 to 34)

對實施例7中所獲得之光轉換用陶瓷複合材料進而於氮氣環境中或還原性氣體環境中(Ar氣+4%氫氣)，以1100~1700℃、4小時或8小時之條件進行熱處理，除此之外，藉由與實施例7相同之方法而製作光轉換用陶瓷複合材料。藉由與實施例7相同之方法，測定所獲得之光轉換用陶瓷複合材料於以460nm波長之光激發之情形時的螢光之主波長、內部量子效率、最大螢光強度、及標準化光束。 The ceramic composite for light conversion obtained in Example 7 is further subjected to heat treatment in a nitrogen atmosphere or a reducing gas atmosphere (Ar gas + 4% hydrogen) at 1100 to 1700 ° C for 4 hours or 8 hours. A ceramic composite for light conversion was produced in the same manner as in Example 7 except for the above. The main wavelength of the fluorescence, the internal quantum efficiency, the maximum fluorescence intensity, and the normalized light beam when the obtained ceramic material for light conversion was excited by light having a wavelength of 460 nm was measured in the same manner as in Example 7.

可知，藉由在氮氣環境中或還原性氣體環境中(Ar氣+4%氫氣)進行熱處理而內部量子效率、相對螢光強度、標準化光束得到改善，特別是於在1400~1600℃下進行熱處理之情形時，改善幅度變大。 It can be seen that the internal quantum efficiency, relative fluorescence intensity, and normalized light beam are improved by heat treatment in a nitrogen atmosphere or a reducing gas atmosphere (Ar gas + 4% hydrogen), particularly at 1400 to 1600 ° C for heat treatment. In the case of the situation, the improvement range becomes larger.

(實施例35) (Example 35)

稱量α-Al2O3粉末(純度為99.99%)49.09g、Y2O3粉末(純度為99.9%)24.31g、Gd2O3粉末(純度為99.9%)2.08g、及CeO2粉末(純度為99.9%)0.39g，將該等原料粉末於乙醇中利用球磨機進行24小時濕式混合後，使用蒸發器對乙醇進行脫介質，從而製備供於煅燒之混合粉末。將所獲得之供於煅燒之混合粉末放入至Al2O3坩鍋，裝入至批次式電爐，並於大氣環境中以1500℃保持3小時進行煅燒，獲得由(Y0.95Gd0.05)3Al5O12：Ce及Al2O3所構成之煅燒粉末。煅燒粉末由(Y0.95Gd0.05)3Al5O12：Ce及Al2O3所構成係藉由X射線繞射分析而確認。 Weighed 49.09 g of α-Al 2 O 3 powder (purity: 99.99%), 24.31 g of Y 2 O 3 powder (purity: 99.9%), 2.08 g of Gd 2 O 3 powder (purity: 99.9%), and CeO 2 powder. (purity: 99.9%) 0.39 g, the raw material powders were wet-mixed in ethanol by a ball mill for 24 hours, and then the ethanol was subjected to deintermediation using an evaporator to prepare a mixed powder for calcination. The obtained mixed powder for calcination was placed in an Al 2 O 3 crucible, charged into a batch type electric furnace, and calcined at 1500 ° C for 3 hours in an atmospheric environment to obtain (Y 0.95 Gd 0.05 ). 3 Al 5 O 12 : calcined powder composed of Ce and Al 2 O 3 . The calcined powder was confirmed by (X 0.95 Gd 0.05 ) 3 Al 5 O 12 :Ce and Al 2 O 3 by X-ray diffraction analysis.

繼而，向所獲得之煅燒粉末添加相對於煅燒粉末100質量%而為11.4質量%之La2O3粉末(純度為99.9%)，除此之外，藉由與實施例30相同之方法而製作光轉換用陶瓷粉末，並算出各結晶相於透光相中之質量比率。又，藉由與實施例1相同之方法，測定所獲得之光轉換用陶瓷複合材料於以460nm波長之光激發之情形時的螢光之主波長、內部量子效率、及最大螢光強度。 Then, La 2 O 3 powder (purity: 99.9%), which was 11.4% by mass based on 100% by mass of the calcined powder, was added to the obtained calcined powder, and was produced in the same manner as in Example 30. The ceramic powder for light conversion was used, and the mass ratio of each crystal phase in the light-transmitting phase was calculated. Further, the main wavelength of the fluorescence, the internal quantum efficiency, and the maximum fluorescence intensity when the obtained ceramic material for light conversion was excited by light having a wavelength of 460 nm was measured in the same manner as in Example 1.

進而，使用場發射穿透電子顯微鏡(日本電子製造之JEM-2100P型)，藉由EDS測定(日本電子製造之UTW型Si(Li)半導體檢測器)而進行透光相與螢光相界面部之組成分析。於圖2中，表示暗視野STEM照片。於圖2(b)所示之後述之比較例7中，於界面部確認到亮點，如表5所示，可知Ce濃度變高至3.9at%。因此，可知，界面部之亮點為因源自Ce之化合物產生之亮點。另一方面，可知，圖2(a)所示之實施例35中未確認到界面部之亮點，Ce濃度亦變低至0.3at%。又，進行螢光相內之組成分析，結果可知，存在0.14at%之La，於螢光相內固溶有La。 Further, a field emission electron microscope (JEM-2100P type manufactured by JEOL Ltd.) was used, and an interface between the light-transmitting phase and the fluorescent phase was performed by EDS measurement (UTW type Si (Li) semiconductor detector manufactured by JEOL Ltd.). The composition of the analysis. In Fig. 2, a dark field STEM photograph is shown. In Comparative Example 7 which will be described later in Fig. 2(b), a bright spot was confirmed at the interface portion, and as shown in Table 5, it was found that the Ce concentration was increased to 3.9 at%. Therefore, it can be seen that the bright spot of the interface portion is a bright spot caused by the compound derived from Ce. On the other hand, in the example 35 shown in Fig. 2 (a), the bright spot of the interface portion was not confirmed, and the Ce concentration was also lowered to 0.3 at%. Further, when the composition analysis in the fluorescent phase was carried out, it was found that 0.14 at% of La was present, and La was solid-solved in the fluorescent phase.

(比較例7) (Comparative Example 7)

不向藉由與實施例35相同之方法而獲得之煅燒粉末追加添加La2O3粉末，而僅使煅燒粉末成形，除此之外，藉由與實施例35相同之方法而獲得比較例7之光轉換用陶瓷複合材料。藉由與實施例1相同之方法，對構成所獲得之光轉換用陶瓷複合材料之結晶相進行鑑定及定量，並算出各結晶相於透光相中之質量比率。又，藉由與實施例1相同之方法，測定所獲得之光轉換用陶瓷複合材料於以460nm波長之光激發之情形時的螢光之主波長、內部量子效率、及最大螢光強度。進而，藉由與實施例35相同之方法，進行透光相與螢光相之界面部之組成分析。 The same procedure as in Example 35 was carried out except that the calcined powder obtained by the same method as in Example 35 was additionally added with La 2 O 3 powder, and only the calcined powder was molded. Ceramic composite material for light conversion. The crystal phase constituting the obtained ceramic composite for light conversion was identified and quantified by the same method as in Example 1, and the mass ratio of each crystal phase in the light-transmitting phase was calculated. Further, the main wavelength of the fluorescence, the internal quantum efficiency, and the maximum fluorescence intensity when the obtained ceramic material for light conversion was excited by light having a wavelength of 460 nm was measured in the same manner as in Example 1. Further, the composition analysis of the interface portion between the light transmitting phase and the fluorescent phase was carried out in the same manner as in Example 35.

Claims (11)

一種光轉換用陶瓷複合材料，由螢光相及透光相所構成，其特徵在於：上述螢光相為含有Ln3Al5O12：Ce(Ln為選自Y、Lu、及Tb中之至少一種元素，Ce為活化元素)之相，且上述透光相為含有LaAl11O18之相。 A ceramic composite material for light conversion, comprising a fluorescent phase and a light transmissive phase, wherein the fluorescent phase comprises Ln 3 Al 5 O 12 :Ce (Ln is selected from the group consisting of Y, Lu, and Tb) A phase of at least one element, Ce is an activating element, and the light transmissive phase is a phase containing LaAl 11 O 18 . 如申請專利範圍第1項之光轉換用陶瓷複合材料，其中，上述螢光相為含有(Ln,La)3Al5O12：Ce(Ln為選自Y、Lu、及Tb中之至少一種元素，Ce為活化元素)之相。 The ceramic composite for light conversion according to the first aspect of the invention, wherein the fluorescent phase contains (Ln, La) 3 Al 5 O 12 :Ce (Ln is at least one selected from the group consisting of Y, Lu, and Tb) The element, Ce is the phase of the active element). 如申請專利範圍第1或2項之光轉換用陶瓷複合材料，其中，上述透光相為含有9~100質量%之LaAl11O18之相。 The ceramic composite for light conversion according to claim 1 or 2, wherein the light transmissive phase is a phase containing 9 to 100% by mass of LaAl 11 O 18 . 如申請專利範圍第1或2項之光轉換用陶瓷複合材料，其中，上述透光相為進而含有選自α-Al2O3及LaAlO3中之至少一種之相。 The ceramic composite for light conversion according to claim 1 or 2, wherein the light transmissive phase further contains at least one phase selected from the group consisting of α-Al 2 O 3 and LaAlO 3 . 如申請專利範圍第1至4項中任一項之光轉換用陶瓷複合材料，其中，上述光轉換用陶瓷複合材料於燒成後在非活性氣體環境或還原性氣體環境中以1000~2000℃受到熱處理。 The ceramic composite for light conversion according to any one of claims 1 to 4, wherein the ceramic composite for light conversion is 1000 to 2000 ° C in an inert gas atmosphere or a reducing gas atmosphere after firing. Heat treated. 一種發光裝置，其具備發光元件、及申請專利範圍第1至5項中任一項之光轉換用陶瓷複合材料。 A light-emitting device comprising a light-emitting element, and a ceramic composite for light conversion according to any one of claims 1 to 5. 一種發光裝置，具備：發光元件，其於波長420~500nm具有波峰；及申請專利範圍第1至5項中任一項之光轉換用陶瓷複合材料，其發出於540~580nm具有主波長之螢光。 A light-emitting device comprising: a light-emitting element having a peak at a wavelength of 420 to 500 nm; and the ceramic composite for light conversion according to any one of claims 1 to 5, which emits a fluorescent light having a dominant wavelength of 540 to 580 nm Light. 如申請專利範圍第6或7項之發光裝置，其中，上述發光元件為發光二極體元件。 The light-emitting device of claim 6 or 7, wherein the light-emitting element is a light-emitting diode element. 一種光轉換用陶瓷複合材料之製造方法，具備如下步驟：煅燒步驟，其係對含有Al源化合物、Ln源化合物(Ln為選自Y、Lu、及Tb中之至少一種元素)、及Ce源化合物之混合粉末進行煅燒；及燒成步驟，其係將對藉由上述煅燒步驟所獲得之煅燒粉末100質量%添加有以氧化物換算計為1~50質量%之La源化合物的含La混合粉末進行燒成。 A method for producing a ceramic composite for light conversion, comprising the steps of: calcining a compound containing an Al source compound, an Ln source compound (Ln is at least one element selected from the group consisting of Y, Lu, and Tb), and a Ce source The mixed powder of the compound is subjected to calcination; and the calcination step is carried out by adding a La-containing mixture of a La source compound in an amount of 1 to 50% by mass in terms of oxide in an amount of 100% by mass of the calcined powder obtained by the calcination step. The powder is fired. 如申請專利範圍第9項之光轉換用陶瓷複合材料之製造方法，其中，於上述燒成步驟後具備熱處理步驟，該熱處理步驟係於非活性氣體環境或還原性氣體環境中以1000~2000℃進行熱處理。 The method for producing a ceramic composite for light conversion according to claim 9, wherein after the baking step, a heat treatment step is provided in an inert gas atmosphere or a reducing gas atmosphere at 1000 to 2000 ° C Heat treatment is performed. 如申請專利範圍第9或10項之光轉換用陶瓷複合材料之製造方法，其中，上述含La混合粉末係於藉由選自壓製成形法、片成形法、及擠壓成形法中之至少一種成形法而成形後被燒成。 The method for producing a ceramic composite for light conversion according to claim 9 or 10, wherein the La-containing mixed powder is at least one selected from the group consisting of a press molding method, a sheet molding method, and an extrusion molding method. After molding, it is formed and fired.
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